Chirality Control in Planar Chiral Cobalt Oxazoline Palladacycles

Doyle J. Cassar,† Hemin Roghzai,† Didier Villemin,‡ Peter N. Horton,§ Simon J. Coles§ and Christopher J. Richards†*

†School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, U.K

‡Laboratoire de Chimie Moleculaire et Thioorganique, UMR CNRS 6507, INC3M, FR 3038,, labex EMC3, ENSICAEN 14050 Caen, France

§EPSRC National Crystallography Service, School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK

Graphic for Table of Contents and Abstract.

ABSTRACT: Palladation of (η5-(S)-2-(4-R-substituted)oxazolinylcyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt(I) with Pd(OAc)2 (R = Me, CH2i-Cy, CH2i-Pr, CH2Ph) resulted exclusively in formation of the (S,Sp)-palladacycle with R = CH2Cy (acetic acid solvent), and up to 13 : 1 selectivity in favour of the (S,Sp)-palladacycle with R = CH2i-Pr (CH2Cl2 solvent). In the latter case diastereomeric purity was achieved by recrystallisation, and the absolute configuration of the new element of planar chirality established by X-ray crystallography. These outcomes contrast with the opposite sense of diastereoselectivity observed for the corresponding R = i-Pr substituted oxazoline which results in the palladacycle (S,Rp)-COP-OAc (acetic acid solvent), these palladation reactions being under either kinetic (S,Sp) or thermodynamic (S,Rp) control. Following conversion to the chloride bridged (S,Sp)-palladacycle dimer (R = CH2Cy), this was employed as a catalyst for the rearrangement of allylic trichloroacetimidates (0.25 mol% catalyst loading, up to 80% ee).

INTRODUCTION

Following the first report on the application of cobalt oxazoline palladacycle 1b (COP-Cl) as a catalyst for the enantioselective rearrangement of N-aryltrifluoroacetimidates,1 there have been many further publications on the successful use of COP complexes 1a/b as either a catalyst2 or reagent3 for other asymmetric transformations. Pentaphenylferrocene based oxazoline complex 2b4 and related imidazolines4,5 have also highlighted the applicability to asymmetric synthesis of palladacycle catalysts based upon bulky ferrocene frameworks.6 Central to the success of these palladacycles is the high diastereoselectivity of C-H activation/palladium-carbon bond formation, as controlled by the heterocyclic auxiliary.7 A notable feature of these reactions is the formation of opposite elements of planar chirality from the i-Pr substituted oxazolines 4 and 5 under identical reaction conditions (Scheme 1).4,8 Furthermore, changing a stereogenic centre substituent from i-Pr to t-Bu in the cobalt-based series also results in a switching of planar chirality, with 3a generated from 6 under the same conditions used for the synthesis of 1a and 2a.9

Scheme 1. Diastereoselective synthesis of known oxazoline-based bulky sandwich-complex based palladacycles.

In this paper we report in detail on the factors influencing the diastereoselectivity of palladation of chiral oxazoline-appended cobalt sandwich complexes, and methods are described for the synthesis of two new diastereomerically pure (S,Sp)-congeners related to 3. These new catalysts, with the potential to be used in several asymmetric transformations, are exemplified by application to the rearrangement of trichloroacetimidates.

RESULTS AND DISCUSSION

Oxazoline synthesis and diastereoselective palladation: Starting from the carboxylic acid 7, and a series of commercially available (S)-amino alcohols, oxazolines 8–11 were synthesised using the same procedure reported previously for 4.10 Following initial formation of an acid chloride with oxalyl chloride, amino alcohol addition gave intermediate hydroxyamides that underwent cyclisation to the required oxazoline moiety on addition of methanesulfonyl chloride (Scheme 2).

Scheme 2. Synthesis of chiral oxazoline-appended cobalt sandwich complexes.

The procedure utilised in the diastereoselective palladation of 4, and also applied to the related oxazolines 5 and 6, involved heating a solution of 4 and Pd(OAc)2 in acetic acid at 95 oC for 30 minutes which resulted in the precipitation of 1a as a single diastereoisomer.8 Application of this protocol to oxazolines 8-11 resulted in the formation of a precipitate in all cases, but following isolation only the product arising from methylenecyclohexyl substituted oxazoline 10 proved to be a palladacycle (Scheme 3, Table 1). This was established readily by the presence of three cyclopentadienyl hydrogen signals in the 1H NMR spectrum compared to the two sets of two diastereotopic cyclopentadienyl hydrogen signals observed in the spectrum of the starting oxazoline. The identity of an oxazoline coordinated palladium as the new cyclopentadienyl ring substituent was confirmed by the reduction in wavenumber of ν(C=N) to 1606 cm-1 from the value of 1655 cm-1 measured for 10, and by the single methyl singlet in the 1H NMR spectrum arising from the acetate ligand. The configuration of the new element of planar chirality was determined as Sp and thus the identity of the palladacycle as 18a by the similarity of the CD spectrum (Figure 1) to that of (S,Sp)-16a for which the configuration of planar chirality was determined later by X-ray crystallography (vide infra).

Figure 1. Circular dichroism spectra of (S,Sp)-16a and (S,Sp)-18a.

Scheme 3. Reaction of oxazolines 4 and 8-11 with palladium acetate and conversion to monomeric hfacac derivatives.

The precipitate obtained from the reaction of oxazoline 9 was identified as palladium acetate adduct 22 (Scheme 4), in part because of the similarity of the cyclopentadienyl region 1H NMR to that of the related trans-chloride-adduct 249 for which two signals are significantly deshielded [5.79 (22) vs. 5.86 (24) and 6.05 (22) vs. 5.98 (24)]. From an examination of the X-ray crystal structure of 24 this may be due to the proximity of the diastereotopic cyclopentadienyl α-hydrogens to the palladium environment perpendicular to the square-plane. The structures of 21 and 23 were assigned by analogy. An attempt to convert an adduct into a palladacycle was performed by re-heating 22 in acetic acid at 95 oC for 30 minutes. This resulted only in oxazoline ring opening and isolation of 25, an outcome consistent with the known Pd(II) promoted ring-opening of an oxazoline by acetate to form an acetate substituted amide.11

Table 1. Reaction of cobalt metallocene oxazolines with palladium acetate.a

Entry

Oxazoline

(substituent)

Solvent

Major

product

Diastereomeric

Ratio (dr)b

Yield

(%)

1

4 (i-Pr)

AcOH

(S,Rp)-1a

>100:1

72

2

8 (Me)

AcOH

21

-

26

3

9 (CH2i-Pr)

AcOH

22

-

97

4

10 (CH2Cy)

AcOH

(S,Sp)-18a

>100:1

70

5

11 (CH2Ph)

AcOH

23

-

89

6

4 (i-Pr)

CH2Cl2

(S,Sp)-12a

2:1

nd

7

8 (Me)

CH2Cl2

(S,Sp)-13a

2.5:1c

nd

8

9 (CH2i-Pr)

CH2Cl2

(S,Sp)-16a

13:1c

73% d

9

10 (CH2Cy)

CH2Cl2

(S,Sp)-18a

1.5:1c

nd

10

11 (CH2Ph)

CH2Cl2

(S,Sp)-20a

1:1c, e

nd

a 95 oC, 30 min. in AcOH or R.T., 16 h. in CH2Cl2. b Determined by 1H NMR spectroscopy. c Determined following conversion to monomeric hfacac complexes. d Diastereomerically pure (S,Sp)-16a (>100:1) achieved by recrystallisation from CH2Cl2/hexane (73% yield). e The major product results from exo-palladation (2.3:1 exo:endo).

Scheme 4. Reaction of oxazolines 8, 9 and 11 with palladium acetate in acetic acid.

Precipitation of these trans-bis(oxazoline) coordination complexes was avoided by carrying out the palladation reactions in dichloromethane at room temperature for 16 hours (Table 1, entries 6-10). Palladacycles were isolated in all cases, and the ratio of (S,Rp)-1a and (S,Sp)-12a (R = i-Pr) was determined directly by 1H NMR. In all other cases the diastereoselectivities were determined by 1H and 19F NMR spectroscopy following conversion to the corresponding hexafluoroacetylacetonate complexes 13c – 20c (Scheme 3). The absolute configuration of the element of planar chirality in the new complexes was made initially by comparison of the cyclopentadienyl proton signals in the mixture, with those observed for diastereomerically pure (S,Sp)-18c obtained for the reaction of (S,Sp)-18a with hexafluoroacetylacetonate, the (S,Rp) and (S,Sp) diastereoisomers each having a characteristic pattern in this region. Modest diastereoselectivities were observed with the Me (8), i-Pr (4) and CH2Cy (10) substituted oxazolines. Palladation of the CH2Ph oxazoline 11 resulted in the additional formation of a palladacycle containing an ortho-carbon/palladium bond on the oxazoline benzyl substituent. This is an example of competitive exo palladation (as opposed to the desired endo palladation), related to that observed previously in the palladation of (R)-4-phenyl-2-oxazolines12a and (S)-4-benzyl-2-methyl-2-oxazoline.12b In contrast, the CH2i-Pr substituted oxazoline 9 resulted in the predominant formation of 16a which was obtained as a single diastereoisomer following recrystallisation from CH2Cl2/hexane. The Sp configuration of the new element of planar chirality was confirmed by an X-ray crystal structure determination (Figure 2).

Figure 2. A molecule of (S,Sp)-16a from X-ray analysis. Principal bond lengths (Å) include: Pd(1)-C(1) 1.970(3), Pd(1)-N(1) 2.029(2), Pd(1)-O(101) 2.134(2), Pd(1)-O(111) 2.051(2). Pd(1)-Pd(2) 2.836(2). Principal angles (o) include: C(1)-Pd(1)-N(1) 80.73(13), O(101)-Pd(1)-O(111) 92.69(10).

Figure 3. Generalised trans-configured acetate-bridged palladacycles containing the same (Sp,Sp) and mixed (Rp,Sp) elements of planar chirality.

The solid state structure of the acetate bridged palladacycle (S,Sp)-16a has a trans orientation of the two bidentate C-N ligands about the Pd2(μ-OAc)2 core. A search of the Cambridge Crystallographic Database revealed 96 palladacycle structures containing this unit, 86 of which are also trans-configured. Of the remaining 10 cis-dimers, 4 adopt this geometry due to geometrical constraints.13 The Pd2(μ-OAc)2 unit of 16a has a Pd-Pd distance of 2.836(2) Å indicative of attractive d8-d8 interaction,14 and the ‘open-book’ or ‘clam’ shape resulting from the bridging ligands is a structural feature found in all acetate-bridged palladacycles. Coupled with the trans geometry, a planar chiral acetate-bridged palladacycle is only feasible with matched Sp,Sp or Rp,Rp configurations, a mixed Sp,Rp configuration resulting in a severe steric clash (Figure 3). In addition to 16a, the 7 reported X-ray crystal structures of planar-chiral acetate-bridged palladacycles are all trans-SpSp or trans-Rp,Rp4,15,16 i.e. consistent with this model. This self-recognition reduces the number of possible dimeric acetate-bridged palladacycles in the solid state, and may be an important factor in the selective precipitation of diastereomerically pure (S,Rp)-1a and (S,Sp)-18a from solution. Acetate-bridged palladacycles have been shown to be monomeric in solution.17 The relative simplicity of the NMR spectra of a mixture of diastereoisomers arising from palladation (e.g. the ratio of (S,Rp)-1a and (S,Sp)-12a was determined directly by 1H NMR), is likely due to these being monomeric in solution at the concentration studied (ca. 5 mM) rather than an extension of dimeric self recognition. For this to be the case, just two (trans-Sp,Sp, trans-Rp,Rp) and none of the remaining four (trans-Sp,Rp, cis-Sp,Sp, cis-Rp,Rp and cis-Sp,Rp), of the six possible dimeric structures would have to be present in solution.

A previous study on the palladation of i-Pr substituted oxazoline 4 in acetic acid at 95 oC revealed a 1:2 ratio of (S,Rp)-1a : (S,Sp)-12a after 5 minutes, as determined by 1H NMR spectroscopy.18 This changed to >20 : 1 after 30 minutes, the isolation of 1a under these conditions resulting from epimerisation and exclusive precipitation of the major thermodynamic diastereoisomer from solution, for which the i-Pr substituent is orientated away from the bulky tetraphenylcyclobutadiene moiety. In contrast, examination by 1H NMR of the palladation of the CH2Cy substituted oxazoline 10 in acetic acid at 95 oC after 5 minutes revealed the presence of (S,Sp)-18a (with no (S,Rp)-17a), and an additional complex for which the 1H NMR data is consistent with a trans-bis(oxazoline) coordination complex. Pure (S,Sp)-18a precipitated from solution after 10 minutes. In this instance, and unlike the outcomes with oxazolines 8, 9 and 11, the presence of the CH2Cy oxazoline substituent does not result in the precipitation from solution of an initially formed coordination complex. In addition, the conformationally more flexible CH2Cy oxazoline substituent does not drive equilibration, unlike the i-Pr substituent of oxazoline 4.

Further examination of the palladation of 4 in dichloromethane at room temperature again revealed a change in diastereoselectivity as a function of time, with the initial preference for 12a (S,Sp) changing to 1a (S,Rp) after prolonged stirring to give a 2:3 (S,Sp)/(S,Rp) thermodynamic ratio after approximately one day (Figure 4). In the early stages of this reaction a trans-bis(oxazoline) intermediate complex was again observed. Repetition, with the addition of approximately 0.6 eq. of dimeric (S,Rp)-1a into the reaction mixture after 3 hours, resulted in a switch in the (S,Sp)/(S,Rp) ratio from 7:3 to 3:7. Further stirring again resulted in the formation of a 2:3 (S,Sp)/(S,Rp) thermodynamic ratio (Figure 5). Examination of the palladation of 10 (R = CH2Cy) under these conditions revealed that the initial ~7 : 3 ratio of (S,Sp)-18a : (S,Rp)-17a determined within the first hour did not change significantly during a 6 day reaction. In contrast, examination of the palladation of CH2i-Pr oxazoline 9 established that the initial ~4 : 1 ratio of (S,Sp)-16a : (S,Rp)-15a determined within the first hour increased over time to give an ~20 : 1 ratio after 30 hours. Although the reactions in dichloromethane avoid the precipitation of a coordination complex, and thus lead to the formation of a palladacycle, the diastereoselectivities observed are, for the most part, low. Selectivity is observed in the early stages of the reaction for the (S,Sp) diastereoisomer, although starting with the i-Pr containing oxazoline 4, epimerisation is again observed resulting, in this instance, in a modest preference for the (S,Rp) diastereoisomer. In contrast the CH2i-Pr substituted oxazoline 9 gives a sufficiently high selectivity that palladation followed by recrystallisation is a practical procedure for the generation of pure (S,Sp)-16a.

Figure 4. Reaction mixture composition vs. time following the addition of Pd(OAc)2 to oxazoline 4 in CH2Cl2 to room temperature.

Figure 5. Reaction mixture composition vs. time following the addition of Pd(OAc)2 to oxazoline 4 in CH2Cl2 to room temperature followed by spiking with additional (S,Rp-1a) after 3 hours.

The conversion of the palladium acetate adducts 21-23 into palladacycles, and the avoidance of oxazoline ring opening, was achieved by heating these in toluene at reflux (Table 2). Complexes 21 and 23, containing the methyl and benzyl oxazoline substituents respectively, resulted in modest selectivity for the Sp diastereoisomer, although in this instance no exo-palladation by-product was formed from the benzyl-substituted oxazoline. The Sp selectivity again predominated with the CH2i-Pr oxazoline containing complex 22 to give (S,Sp)-16a/(S,Rp)-17a in a ratio of 8:1, recrystallisation again resulting in the isolation of the major product as a single diastereoisomer.

Table 2. Conversion of palladium acetate adducts 21-23 into palladacyclesa

Entry

Complex

(substituent)

Solvent

Major

product

Diastereomeric

Ratio (dr)b

1

21 (Me)

PhMe

(S,Sp)-14a

1.5:1

2

22 (CH2i-Pr)

PhMe

(S,Sp)-16a

8:1c

3

23 (CH2Ph)

PhMe

(S,Sp)-20a

1.8:1

a Heated at reflux, 2 h. in PhMe. b Determined following conversion to monomeric hfacac complexes. c Diastereomeric purity (>100:1) achieved by recrystallisation from CH2Cl2/hexane.

Palladation with palladium acetate has been shown to occur by acetate-assisted concerted metallation deprotonation (CMD).19 The kinetic preference for the formation of (S,Sp)-palladacycles is the same sense of selectivity observed in the lithiation20 and palladation21 of related ferrocenyloxazolines, and is also observed for the lithiation22 and palladation4 of pentaphenylferrocenyloxazoline 5.23 In the latter reaction, precipitation of this kinetic product from the reaction mixture prevents the possibility of isomerisation to the alternative (S,Rp)-isomer. The faster formation of the (S,Sp)-diastereoisomers may be accounted for by a transition state model in which formation of the palladium-carbon bond by exo approach of the metal is not restricted by the oxazoline substituent, as represented by 25 (Figure 6). This contrasts with 26, the transition state leading to the (S,Rp)-diastereoisomers, in which the oxazoline 4-substituent is now proximate to the forming palladium-carbon bond, increasing the energy of this step. The palladation reaction is reversible in both acetic acid and dichloromethane, a viable pathway for this process being an acetate-mediated retro-CMD step followed by repalladation. Only in the case of the isopropyl substituted oxazoline does this result in reversal of the initial kinetic selectivity, and with acetic acid as solvent this is sufficiently pronounced that, following precipitation, (S,Rp)-1a is isolated as a single diastereoisomer. Only for the palladation of the oxazolines containing a CH2Cy substituent (10) or a CH2i-Pr substituent (9), can this kinetic selectivity lead to the isolation of a pure diastereoisomer, albeit in different solvents. This further illustrates that achieving high diastereoselectivity in these palladation reactions is a subtle balance between kinetic and thermodynamic control, coupled with the differences in the solubility of the product, and that of the initially formed trans-bis(oxazoline) coordination complex.

Figure 6. The basis of kinetic control via diastereoisomeric transition states 25 and 26.

Asymmetric catalysis: As chloride-bridged complex (S,Rp)-1b has been applied successfully as a catalyst for the enantioselective rearrangement of trichloroacetimidates, comparison to at least one of the new palladacycles generated in this work required the conversion of (S,Sp)-16a and (S,Sp)-18a into the corresponding chloride-bridged palladacycles, (S,Sp)-16b and (S,Sp)-18b respectively. This was achieved readily by stirring the acetate-bridged palladacycles with an aqueous acetone solution of sodium chloride (Scheme 5). Both were obtained as a mixture of isomers containing cis and trans orientations of the two bidentate C-N ligands about the Pd2(μ-Cl)2 core, a dimeric structure which is maintained in solution.

Scheme 5. Synthesis of chloride-bridged dimers 16b and 18b.

Scheme 6. Catalyst comparison in the rearrangement of (E)-trichloroacetimidates 27a/b.

Table 3. Catalyst comparison in the rearrangement of (E)-trichloroacetimidates 27a/b.

Entry

Substrate

Catalyst

Product/

Yielda

Config.

eeb

1

27a

(S,Sp)-18b

28a 79%

(R)

72

2

27a

(R,Sp)-1b

28a 93%

(R)

92

3

27b

(S,Sp)-18b

28b 81%

(R)

80c

4

27b

(R,Sp)-1b

28b 93%

(R)

89

a Isolated by column chromatography. b Determined by chiral HPLC. c Determined by chiral HPLC following trichloroacetamide hydrolysis and reaction of the resulting allylamine with p-BrC6H4COCl.

The conditions used for the catalysed rearrangement of trichloroacetimidates 27a/b were those developed previously in the group using just 0.25 mol% of catalyst in acetonitrile at 70 oC for 48 hours (Scheme 6).2g Under these conditions with substrate 27a, catalyst (S,Sp)-18b resulted in a lower yield and ee compared to (R,Sp)-1b (Table 3, entries 1 and 2), results mirrored with a second trichloroacetimidate substrate 27b (entries 3 and 4). That all the rearranged products had the same configuration (R) confirmed that the element of planar chirality (Sp for both catalysts) dominates the stereocontrol, as required by the model of the origin of enantioselectivity in these reactions.2f As (S,Sp)-18b and (R,Sp)-1b are not diastereoisomers, due to their different oxazoline substituents, the terms matched and mismatched must be used with caution. However, when considered with the results of a previous study on the comparison of catalysts derived by treatment of (R,Sp)-1b or (S,Sp)-3b with silver trifluoroacetate for the rearrangement of N-(4-methoxyphenyl)trifluoroacetimidates9 [(R,Sp)-1b: 72-78% yield, 81-95% ee. (S,Sp)-3b: 24-64% yield, 36-58% ee], there is a clear trend in favour of the (R,Sp) diastereoisomer with respect to both yield and enantioselectivity. Whether this is the case for other palladacycle catalysed reactions remains an area of ongoing study.

CONCLUSION

For a range of chiral oxazoline-appended cobalt sandwich complexes of S-configuration, reaction with palladium acetate in acetic acid at 95 oC results in a diastereomerically pure (S,Sp)-palladacycle where the oxazoline substituent is CH2Cy, With oxazolines containing Me, i-Bu or Bn substituents palladation was not observed due to the precipitation of the corresponding trans-bisoxazoline palladium diacetate complexes. On changing the reaction solvent to dichloromethane, palladation at room temperature was observed with all the (S)-oxazolines used (substituents = Me, i-Pr, i-Bu, CH2Cy, Bn), but high selectivity was observed in only one case (i-Bu, dr = 13 : 1). Recrystallisation gave the diastereomerically pure (S,Sp)-palladacycle. Examination of the palladation reactions in CH2Cl2 revealed epimerisation from (S,Sp) to (S,Rp) with time, consistent with the (S,Sp) isomer being kinetically preferred, and (S,Rp) being thermodynamically preferred. The two new (S,Sp)-palladacycles add to the two known cobalt oxazoline palladacycles (R = i-Pr = S,Rp and R = t-Bu = S,Sp) aiding the determination of potential matched and mismatched pairings in palladacycle catalysed reactions. Examination of the rearrangement of the allylic trichloroacetimidates points to (S,Rp) and (S,Sp)-systems being the matched and mismatched pairing respectively, with chirality control dominated by the element of planar chirality.

EXPERIMENTAL SECTION

General Remarks: All reactions were carried out under an argon atmosphere unless otherwise stated. Toluene was dried over sodium and benzophenone ketyl. Dichloromethane was dried over CaCl2. (5-Carboxycyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) was prepared as reported previously.10 Oxazolines 4 and 8 have been reported previously.8,9

General method for oxazoline ligand preparation: A flask was charged with (5-carboxycyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) (1 eq.) and dissolved in CH2Cl2 (10 mL/mmol). Oxalyl chloride (2 eq.) and dimethylformamide (3 drops) were added sequentially. After 30 minutes the solution was concentrated in vacuo, redissolved in CH2Cl2 and re-concentrated in vacuo to give the crude acid chloride. To a solution of amino alcohol (1.4 eq.) and triethylamine (6 eq.) in CH2Cl2 (5 mL/mmol) was added a solution of the crude acid chloride in CH2Cl2 (10 mL/mmol) via cannula. The resulting solution was maintained at rt and after 2 h the mixture was cooled to 0 °C in an ice bath. Methanesulfonyl chloride (2.5 eq.) was then added in one portion and the resulting solution was allowed to warm to rt. After 16 h the solution was washed with saturated aqueous sodium bicarbonate and then with brine. The organic layer was separated, dried over MgSO4, filtered, and concentrated in vacuo. Purification by column chromatography on silica eluting with hexanes/EtOAc (9:1) yielded the required product.

5-(S)-2-(4-Isobutyl)oxazolinylcyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) 9: General method followed using (5-carboxycyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) (2.65 g, 5.05 mmol) and (S)-leucinol (0.90 mL, 7.04 mmol). Purification by column chromatography on silica eluting with hexanes/EtOAc (9:1) gave the product as a gold coloured solid (2.43g, 79 %).

Mp: 116 oC. [α]23D -114 (c 0.14, CH2Cl2). IR (film): νmax = 1655 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.42-7.32 (8H, m, ArH), 7.21-7.07 (12H, m, ArH), 5.09 (1H, brs, CpH), 5.02 (1H, brs, CpH), 4.70 (1H, brs, CpH), 4.62 (1H, brs, CpH), 3.70-3.60 (2H, m, CH), 3.30-3.20 (1H, m, CH), 1.63-1.53 (1H, m, CH), 1.36-1.26 (1H, m, CH), 0.95-0.88 (1H, m, CH), 0.83 (3H, d, J 6.3, CH3), 0.81 (3H, d, J 6.3, CH3). 13C NMR (, 126 MHz, CDCl3): 135.4 (ArC) 128.9 (ArC), 127.9 (ArC), 126.4 (ArC), 86.4 (CpC), 85.0 (CpC), 84.6 (CpC), 84.5 (CpC), 82.1 (CpC), 76.0 (C4Ph4), 72.1 (CH), 64.6 (CH), 45.3 (CH), 25.5 (CH), 23.1 (CH), 22.8 (CH), (C=N not observed). High-resolution MS (m/z, ESI+) found for MH+ = 606.2197, calcd for C40H37CoNO 606.2202.

5-(S)-2-(4-Cyclohexylmethyl)oxazolinylcyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) 10: General method followed using (5-carboxycyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) (0.965 g, 1.84 mmol) and (S)-cyclohexylalaninol (0.406 g, 2.58 mmol). Purification by column chromatography on silica eluting with hexanes/EtOAc (9:1) gave the product as an orange solid (0.868 g, 73%).

Mp: 175 oC. [α]21D -33 (c 0.06, CH2Cl2). IR (film): νmax = 1656 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.39–7.32 (8H, m, ArH), 7.17-7.05 (12H, m, ArH), 5.06 (1H, brs, CpH), 4.99 (1H, brs, CpH), 4.66 (1H, brs, CpH), 4.58 (1H, brs, CpH), 3.72–3.64 (1H, m, CH), 3.64–3.58 (1H, m, CH), 3.21 (1H, t, J 7.5, CH), 1.66–1.52 (4H, m, CH), 1.30–1.02 (7H, m, CH), 0.83–0.72 (2H, m, CH); 13C NMR (, 126 MHz, CDCl3): 159.4 (C=N), 134.3 (ArC), 127.9 (ArC), 126.9 (ArC), 125.4 (ArC), 85.4 (CpC), 83.6 (CpC), 83.4 (CpC), 81.0 (CpC), 74.9 (C4Ph4), 71.2 (CH), 63.0 (CH), 43.0 (CH), 33.8 (CH), 32.4 (CH), 32.4 (CH), 25.9 (CH), 25.6 (CH), 25.2 (CH). High-resolution MS (m/z, ESI+) found for MH+ = 646.2506, calcd for C43H41CoNO 646.2515.

5-(S)-2-(4-Benzyl)oxazolinylcyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) 11: General method followed using (5-carboxycyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) (1.01 g, 1.93 mmol) and (S)-phenylalaninol (0.409 g, 2.70 mmol). Purification by column chromatography on silica eluting with hexanes/EtOAc (9:1) gave the product as a yellow solid (1.16 g, 94 %).

Mp: 131 oC. [α]19D -66 (c 0.10, CH2Cl2). IR (film): νmax = 1655 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.49-7.41 (8H, m, ArH), 7.33-7.17 (15H, m, ArH), 7.17-7.12 (2H, d, J 7.1, ArH), 5.18 (1H, brs, CpH), 5.10 (1H, brs, CpH), 4.81 (1H, brs, CpH), 4.73 (1H, brs, CpH), 4.07-3.92 (1H, m, CH), 3.62-3.42 (2H, m, CH), 3.00 (1H, dd, J 13.7, 4.9, CHHPh), 2.25 (1H, dd, J 13.7, 9.5, CHHPh). 13C NMR (, 126 MHz, CDCl3): 161.4 (C=N), 138.7 (ArC), 135.4 (ArC), 129.1 (ArC), 129.1 (ArC), 128.6 (ArC), 128.1 (ArC), 126.6 (ArC), 126.4 (ArC), 86.6 (CpC), 84.8 (CpC), 84.8 (CpC), 82.2 (CpC), 76.1 (C4Ph4), 71.3 (CH), 67.8 (CH), 41.8 (CH). High-resolution MS (m/z, ESI+) found for MH+ = 640.2043, calcd for C43H35CoNO 640.2045.

General method for palladation of oxazoline ligands: A flask was charged with the oxazoline ligand (1 eq.) and dissolved in the required solvent (5 mL/mmol). To this solution palladium(II) acetate (1 eq.) was added in one portion. The flask was sealed and the solution was stirred at the required temperature for the allotted time. The products were isolated either by filtration or by removal of the solvent in vacuo.

Di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-isobutyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 16a:

General method for palladation was followed using 5-(S)-2-(4-iso-butyl)oxazolinylcyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) 9 (0.050 g, 0.08 mmol) and palladium(II) acetate (0.019 g, 0.08 mmol) in CH2Cl2 (0.5 mL). The solution was stirred at rt for 16h. The solvent was removed in vacuo to yield the crude product as an orange solid, for which the ration of Sp:Rp was determined in a separate experiment as 13:1 by conversion to the corresponding hfacac monomer (see below). Recrystallisation from CH2Cl2/hexane gave 16a as a single diastereoisomer (0.046 g, 73%).

Mp: 266 oC. Anal. Found: C 65.59; H 5.04; N 1.91. Calcd for C84H76Co2N2O6Pd2: C 65.50; H 4.98; N 1.82. [α]19D -721 (c 0.12, CH2Cl2). IR (film): νmax = 1605 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.67–7.60 (16H, m, ArH), 7.24–7.19 (24H, m, ArH), 4.65 (2H, brs, CpH), 4.49 (2H, brs, CpH), 4.07 (2H, t, J 2.4, CpH), 4.00–3.92 (2H, m, CH), 3.54 (2H, t, J 7.7, CH), 3.05–2.95 (2H, m, CH), 2.00 (6H, s, CH3), 1.41-1.31 (2H, m, CH), 1.15–1.04 (2H, m, CH), 0.71 (6H, d, J 6.6, CH3), 0.67 (6H, d, J 6.6, CH3), 0.19 (2H, ddd, J 13.6, 11.3, 4.7, CH). 13C NMR (, 126 MHz, CDCl3): 180.9 (MeCO2), 172.1 (C=N), 135.9 (ArC), 129.2 (ArC), 128.0 (ArC), 126.4 (ArC), 97.7 (CpC), 86.9 (CpC), 85.7 (CpC), 83.3 (CpC), 76.9 (CH), 76.5 (C4Ph4), 59.7 (CH), 42.8 (CH), 25.4 (CH), 24.0 (CH), 23.4 (CH), 21.8 (CH).

Formation of trans-bis(oxazoline) coordination complex 22: The general method for palladation was followed using 5-(S)-2-(4-iso-butyl)oxazolinylcyclopentadienyl)(4-tetraphenylcyclobutadiene)cobalt(I) 9 (0.500 g, 0.83 mmol) and palladium(II) acetate (0.186 g, 0.83 mmol) in acetic acid (1 mL). Heating the solution at 95 °C for 30 minutes followed by cooling and isolation by filtration gave the product as an orange solid (0.573 g, 97 %).

Mp: 188-190 oC. Anal. Found: C 70.08; H 5.35; N 1.85. Calcd for C84H78Co2N2O6Pd: C 70.27; H 5.48; N 1.95. [α]24D +151 (c 0.2, CH2Cl2). IR (film): νmax = 1634 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.46–7.33 (16H, m, ArH), 7.24–7.12 (24H, m, ArH), 6.05 (2H, vbrs, CpH), 5.79 (2H, brs, CpH), 4.90–4.57 (4H, m, CpH), 3.75–3.64 (2H, m, CH), 3.63–3.56 (2H, m, CH), 3.27–3.18 (2H, m, CH), 3.08–2.96 (2H, m, CH), 2.05 (6H, brs, CH3), 1.58–1.42 (4H, m, CH), 1.02–0.86 (12H, m, CH3). 13C NMR (, 126 MHz, CDCl3): 175.6 (MeCO2), 165.5 (C=N), 135.5 (ArC), 129.0 (ArC), 128.0 (ArC), 126.6 (ArC), 86.2 (CpC), 85.4 (CpC), 84.1 (CpC), 76.4 (C4Ph4), 72.4 (CH), 43.2 (CH), 26.0 (CH), 23.9 (CH), 22.4 (CH), 21.7 (CH), 21.0 (CH).

Conversion of trans-bis(oxazoline) coordination complex 22 into amide 25: A flask charged with 22 (0.080 g, 0.06 mmol) dissolved in AcOH (5 mL) and was heated to 90 °C for 4 h. On completion, the solvent was removed in vacuo. The crude residue was redissolved in CH2Cl2 (5 mL) and washed with aqueous sodium hydrocarbonate solution (5 mL). The organic layer was collected, dried over MgSO4 and the solvent was removed in vacuo. Purification by column chromatography on silca eluting with CH2Cl2/EtOAc (9:1) gave the product as an orange oil (0.016 g, 22 %).

[α]26D +24.4 (c = 0.16, CH2Cl2). IR (film): νmax = 1739 (C=O), 1644 (C=O) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.45 (8H, d, J 7.3, ArH), 7.32–7.19 (12H, m, ArH), 5.22 (1H, brd, J 8.4, NH), 5.01 (2H, brs, CpH), 4.67 (2H, brs, CpH), 4.09–4.03 (1H, m, CH), 3.92 (1H, dd, J 11.2, 5.6, CH), 3.67 (1H, dd, J 11.2, 4.7, CH), 2.01 (3H, s, CH3), 1.49–1.38 (1H, m, CH), 1.11–1.02 (1H, m, CH), 0.99–0.91 (1H, m, CH), 0.87 (3H, t, J 7.0, CH3), 0.85 (3H, t, J 7.0, CH3). 13C NMR (, 126 MHz, CDCl3): 171.3 (C=O), 165.8 (C=O), 135.4 (ArC), 128.9 (ArC), 128.3 (ArC), 126.9 (ArC), 90.8 (CpC), 86.9 (CpC), 86.6 (CpC), 82.3 (CpC), 82.0 (CpC), 76.3 (C4Ph4), 66.0 (CH), 47.0 (CH), 40.5 (CH), 24.8 (CH), 22.9 (CH), 22.7 (CH), 21.1 (CH). High-resolution MS (m/z, ESI+) found for MH+ = 666.2413, calcd for C42H41CoNO3 666.2413.

Conversion of trans-bis(oxazoline) coordination complex 22 into 16a: A flask was charged with complex 22 (0.500 g, 0.35 mmol) dissolved in toluene (2 mL). The solution was heated at reflux for 2 h. On completion, the solution was cooled and the solvent was removed in vacuo to yield the product as an orange solid (0.252 g, 94 %). The 10:1 ratio of isomer was determined following conversion to the corresponding hfacac complexes. Recrystallisation from CH2Cl2/hexane gave diastereomerically pure 16a.

Di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-cyclohexylmethyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 18a: General method for palladation was followed using 5-(S)-2-(4-cyclohexylmethyl)oxazolinylcyclopentadienyl)-(4-tetraphenylcyclobutadiene)cobalt(I) 10 (0419 g, 0.65 mmol) and palladium(II) acetate (0.146 g, 0.65 mmol) in acetic acid (1 mL). Heating the solution at 95 °C for 30 minutes yielded the product (after filtration) as an orange solid (0.370 g, 70 %).

Mp: 248 oC (dec.). Anal. Found: C 66.77; H 5.04; N 1.91. Calcd for C90H84Co2N2O6Pd2: C 66.71; H 5.23; N 1.73. [α]19D -407 (c 0.10, CH2Cl2). IR (film): νmax = 1606 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.63–7.56 (16H, m, ArH), 7.23–7.12 (24H, m, ArH), 4.55 (2H, brs, CpH), 4.39 (2H, brs, CpH), 3.96 (2H, brs, CpH), 3.88 (2H, t, J 8.5, CH), 3.47 (2H, t, J 7.5, CH), 3.02–2.86 (2H, m, CH), 1.92 (6H, s, CH3), 1.72–1.17 (12H, m, CH), 1.15–0.90 (6H, m, CH), 0.84–0.49 (6H, m, CH), 0.14-0.02 (2H, m, CH). 13C NMR (, 126 MHz, CDCl3): 180.9 (MeCO2), 172.1 (C=N), 135.9 (ArC), 129.2 (ArC), 128.0 (ArC), 126.3 (ArC), 86.7 (CpC), 85.7 (CpC), 83.3 (CpC), 77.1 (CH), 76.5 (C4Ph4), 59.2 (CH), 41.2 (CH), 34.8 (CH), 33.8 (CH), 32.2 (CH), 26.4 (CH), 25.9 (CH), 24.0 (CH).

Di-μ-chlorobis[(η5-(S)-(Sp)-2-(2’-4’-isobutyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 16b:

A flask was charged with di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-iso-butyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]-dipalladium(II) 16a (0.020 g, 0.01 mmol) dissolved in acetone (0.5 mL). To this solution was added a 2M NaCl solution (0.06 mL, 0.12 mmol) and the solution was vigorously stirred at rt for 4 h, after which time a precipitate had formed. The precipitate was collected by filtration, washed with water and acetone and dried under vacuum to yield the product as a yellow solid (0.007 g, 36 %).

Mp: 183-185 oC. Anal. Found: C 62.81; H 5.15; N 1.76. Calcd for C80H70Cl2Co2N2O2Pd2.2H2O: C 62.84; H 4.88; N 1.83. [α]25D -1222 (c 0.19 CH2Cl2). IR (film): νmax = 1601 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3, ~1:1 ratio of cis/trans isomers): 7.72–7.65 (16 H m, ArH), 7.64–7.57 (16H, m, ArH), 7.31-7.16 (48H, m, ArH), 4.77 (2H, dd, J 2.5, 1.1, CpH), 4.71 (2H, dd, J 2.8, 1.0, CpH), 4.70–4.66 (4H, m, CpH), 4.58 (2H, t, J 7.8, CH), 4.52 (2H, t, J 8.7, CH), 4.46 (2H, t, J 2.5, CpH), 4.32 (1H, t, J 2.5, CpH), 3.93 (2H, dd, J 8.3, 6.4, CH), 3.89–3.72 (6H, m, CH), 1.81 (2H, ddd, J 12.9, 10.1, 2.3, CH), 1.55–1.48 (2H, m, CH), 1.37–1.24 (4H, m, CH), 0.94–0.77 (24H, m, CH3), 0.43-0.32 (4H, m, CH). 13C NMR (, 126 MHz, CDCl3): 173.8 (C=N), 173.7 (C=N), 135.8 (ArC), 135.8 (ArC), 129.5 (ArC), 129.4 (ArC), 128.2 (ArC), 128.1 (ArC), 126.6 (ArC), 126.5 (ArC), 100.1 (CpC), 99.9 (CpC), 89.0 (CpC), 88.8 (CpC), 83.2 (CpC), 82.0 (CpC), 77.7 (CH), 76.7 (CH), 76.5 (C4Ph4), 76.3 (C4Ph4), 60.8 (CH), 60.6 (CH), 43.6 (CH), 43.3 (CH), 25.7 (CH), 25.6 (CH), 23.8 (CH), 23.7 (CH), 21.5 (CH), 21.4 (CH).

Di-μ-chlorobis[(η5-(S)-(Sp)-2-(2’-4’-cyclohexyl)oxazolinylmethyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 18b:

A flask was charged with di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-cyclohexylmethyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)-cobalt(I)]dipalladium(II) 18a (0.050 g, 0.03 mmol) dissolved in acetone (1 mL). To this solution was added a 2M NaCl solution (0.2 mL, 0.4 mmol) and the solution was vigorously stirred at rt for 4 h after which time a precipitate had formed. The precipitate was collected by filtration, washed with water and acetone and dried under vacuum to yield the product as a yellow solid (0.024 g, 47 %).

Mp: 203 oC. Anal. Found: C 64.35; H 4.74; N 1.88. Calcd for C86H78Cl2Co2N2O2Pd2.2H2O: C 64.19; H 5.14; N 1.74. [α]25D -1113 (c 0.34, CH2Cl2). IR (film): νmax = 1601 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3, ~2:3 ratio of isomers): 7.71–7.65 (13H, m, ArH), 7.64–7.58 (19H, m, ArH), 7.28-7.16 (48H, m, ArH), 4.76 (1.6H, dd, J 2.3, 1.1, CpH), 4.71 (2.4H, dd, J 2.8, 1.0, CpH), 4.71–4.65 (4H, m, CpH), 4.63–4.55 (2.4H, m, CH), 4.52 (1.6H, t, J 8.7, CH), 4.46 (2.4H, t, J 2.5, CpH), 4.34 (1.6H, t, J 2.6, CpH), 3.93 (1.6H, dd, J 8.3, 6.4, CH), 3.89–3.74 (6.4H, m, CH), 1.95-0.78 (48H, m, CH), 0.44–0.25 (4H, m, CH). 13C NMR (, 126 MHz, CDCl3): 173.8 (C=N), 173.7 (C=N), 135.8 (ArC), 135.8 (ArC), 129.5 (ArC), 129.4 (ArC), 128.2 (ArC), 128.1 (ArC), 126.6 (ArC), 126.5 (ArC), 99.9 (CpC), 99.4 (CpC), 89.2 (CpC), 89.1 (CpC), 85.9 (CpC), 85.4 (CpC), 83.3 (CpC), 82.1 (CpC), 77.4 (CH), 77.3 (CH), 76.4 (C4Ph4), 76.3 (C4Ph4), 60.4 (CH), 60.2 (CH), 42.3 (CH), 41.9 (CH), 35.1 (CH), 34.2 (CH), 32.2 (CH), 31.1 (CH), 26.7 (CH), 26.7 (CH), 26.6 (CH), 26.5 (CH), 26.4 (CH), 26.2 (CH).

Hexafluoroacetylacetonate[(η5-(S)-(Sp)-2-(2’-(4’-iso-butyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]palladium(II) 16c: A flask was charged with di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-iso-butyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 16a (0.010 g, 0.01 mmol) and sodium hexafluroacetylacetonate (0.014 g, 0.06 mmol) in acetone/water (2:1 solution, 2 mL). The solution was stirred vigorously for 16 h after which time a precipitate had formed. The solution was diluted with CH2Cl2 (5 mL) and washed with water (5 mL). The organic layer was collected, dried over MgSO4 and the solvent was removed in vacuo to yield the product as an orange solid (0.010 g, 83%).

Mp: 253 oC. Anal. Found: C 58.71; H 4.05; N 1.68. Calcd for C45H36CoF6NO3Pd: C 58.87; H 3.96; N 1.53. [α]25D -919 (c 0.16, CH2Cl2). IR (film): νmax = 1600 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.63–7.57 (8H, m, ArH), 7.27–7.22 (4H, m, ArH), 7.21-7.15 (8H, m, ArH), 5.92 (1H, s, CH), 4.97 (1H, dd, J 2.3, 0.9, CpH), 4.80 (1H, dd, J 2.6, 0.8, CpH), 4.64 (1H, t, J 2.5, CpH), 4.59 (1H, t, J 8.3, CH), 3.91–3.75 (2H, m, CH), 1.85–1.72 (1H, m, CH), 1.40–1.30 (1H, m, CH), 0.84 (6H, d, J 7.0, CH3), 0.57–0.46 (1H, m, CH). 13C NMR (, 126 MHz, CDCl3): 174.8 (C=N), 174.1 (CO, app d, JC-F 4.7), 173.8 (CO, app d, JC-F 4.8), 135.8 (ArC), 129.2 (ArC), 127.9 (ArC), 126.6 (ArC), 118.9 (CF, app d, JC-F 55.7), 116.7 (CF, app d, JC-F 55.1), 100.0 (CpC), 90.2 (CpC), 88.4 (CpC), 86.6 (CpC), 81.7 (CpC), 77.2 (CH), 76.5 (C4Ph4), 60.3 (CH), 43.8 (CH), 25.4 (CH), 23.6 (CH), 21.3 (CH). 19F NMR (, 471 MHz, CDCl3): -74.69, -75.63.

Hexafluoroacetylacetonate[(η5-(S)-(Sp)-2-(2’-(4’- cyclohexylmethyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclo- butadiene)cobalt(I)]palladium(II) 18c: A flask was charged with di-μ-acetatobis[(η5-(S)-(Sp)-2-(2’-4’-cyclohexylmethyl)oxazolinyl)cyclopentadienyl, 1-C, 3’-N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium(II) 18a (0.030 g, 0.02 mmol) and sodium hexafluroacetylacetonate (0.043 g, 0.19 mmol) in acetone/water (2:1 solution, 2 mL). The solution was stirred vigorously for 16 h after which time a precipitate had formed. The solution was diluted with CH2Cl2 (5 mL) and washed with water (5 mL). The organic layer was collected, dried over MgSO4 and the solvent was removed in vacuo to yield the product as an orange solid (0.031 g, 86%).

Mp: 204 oC. Anal. Found: C, 60.25; H, 4.36; N 1.81. Calcd for C48H40CoF6NO3Pd: C, 60.16; H, 4.22; N, 1.46. [α]25D -532 (c 0.52, CH2Cl2). IR (film): νmax = 1601 (C=N) cm-1. 1H NMR (, 500 MHz, CDCl3): 7.62–7.54 (8H, m, ArH), 7.25–7.20 (4H, m, ArH), 7.19–7.13 (8H, m, ArH), 5.88 (1H, s, CH), 4.94 (1H, dd, J 2.3, 1.0, CpH), 4.77 (1H, dd, J 2.6, 1.0, CpH), 4.60 (1H, t, J 2.6, CpH), 4.60–4.53 (1H, m, CH), 3.91–3.81 (1H, m, CH), 3.80–3.73 (1H, m, CH), 1.90–1.80 (1H, m, CH), 1.76–1.57 (3H, m, CH), 1.52–1.44 (1H, m, CH), 1.37–0.78 (7H, m, CH), 0.51–0.40 (1H, m, CH). 13C NMR (, 126 MHz, CDCl3): 174.7 (C=N), 174.0 (CO, app d, JC-F 10.0), 173.8 (CO app d, JC-F 10.6), 135.8 (ArC), 129.2 (ArC), 127.9 (ArC), 126.6 (ArC), 118.9 (CF, app d, JC-F 54.9), 116.7 (CF, app d, JC-F 53.9), 100.0 (CpC), 90.2 (CpC), 88.4 (CpC), 86.6 (CpC), 81.7 (CpC), 76.5 (C4Ph4), 59.9 (CH), 42.0 (CH), 34.9 (CH), 34.2 (CH), 32.0 (CH), 31.1 (CH), 26.5 (CH), 26.0 (CH). 19F NMR (, 471 MHz, CDCl3): -74.69, -75.56.

X-ray details A suitable crystal of (S,Sp)-16a was selected and data collected following a standard method,24 on a Rigaku AFC12 goniometer at 100K equipped with an enhanced sensitivity (HG) Saturn724+ detector mounted at the window of an FR-E-Superbright molybdenum anode generator with HF Varimax optics (100μm focus). Cell determination, data collection,data reduction, cell refinement and absorption correctionwere carried out using CrystalClear.25 Structure solutionand refinement using SHELX programs.26

Crystal data for (S,Sp)-16a : C84H76Co2N2O6Pd2.0.5(H2O),M = 1549.13, red blade, a = 10.333(9), b = 11.314(2), c = 16.307(13) Å, α = 71.68(5),β = 88.83(4),γ = 76.54(4),V = 1757(2) Å3, T = 100(2) K, space group P1, Z = 1, μ = 1.025 mm1, reflections collected = 19659, independent reflections = 12074, Flack parameter = 0.018(6), R1 = 0.0221, wR2 = 0.0.529 [F2> 2(F2)], R1 = 0.0227, wR2 = 0.0533 (all data).

ASSOCIATED CONTENT

Supporting Information. CCDC1055821 contains supplementary X-ray crystallographic data for (S,Sp)-16a. This data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, Union Road, Cambridge, CB2 1EZ; fax(+44) 1223-336-033 or email: deposit@ccdc.cam.ac.uk. Methods for the determination of palladation diastereoselectivies and catalysis product enantioselectivities, 1H/13C/19F spectra, and details of the X-ray structure search on Pd2(μ-OAc)2 containing palladacycles. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: Chris.Richards@uea.ac.uk

Notes

The authors declare no competing financial interest.

ACKNOWLEDMENTS

For financial support we thank the ISCE-Chem & INTERREGIVa programme (D.C.). We thank Niccole L. Sanders (UEA) for preliminary experiments, Myles Cheesman (UEA) for assistance with the CD spectra, and Laszlo Fabian (UEA) for the CCDC search. We also thank the EPSRC National Mass Spectrometry Centre (University of Wales, Swansea).

REFERENCES

(1)Overman, L. E.; Owen, C. E.; Pavan, M. M.; Richards, C. J. Org. Lett. 2003, 5, 1809-1812.

(2)(a) Anderson, C. E.; Overman, L. E. J. Am. Chem. Soc. 2003, 125, 12412-12413. (b) Kirsch, S. F.; Overman, L. E. J. Am. Chem. Soc. 2005, 127, 2866-2867. (c) Kirsch, S. F.; Overman, L. E. J. Org. Chem. 2005, 70, 2859-2861. (d) Lee, E. E.; Batey, R. A. J. Am. Chem. Soc. 2005, 127, 14887-14893. (e) Kirsch, S. F.; Overman, L. E.; White, N. S. Org. Lett. 2007, 9, 911-913 (f) Watson, M. P.; Overman, L. E.; Bergman, R. G. J. Am. Chem. Soc. 2007, 129, 5031-5044. (g) Nomura, H.; Richards, C. J. Chem. Eur. J. 2007, 13, 10216-10224. (h) Overman, L. E.; Roberts, S. W.; Sneddon, H. F. Org. Lett. 2008, 10, 1485-1488. (i) Rodrigues, A.; Lee, E. E.; Batey, R. A. Org. Lett. 2010, 12, 260-263. (j) Cannon, J. S.; Kirsch, S. F.; Overman, L. E. J. Am. Chem. Soc. 2010, 132, 15185-15191. (k) Cannon, J. S.; Kirsch, S. F.; Overman, L. E.; Sneddon, H. F. J. Am. Chem. Soc. 2010, 132, 15192-15203. (l) Cannon, J. S.; Olson, A. C.; Overman, L. E.; Solomon, N. S. J. Org. Chem. 2012, 77, 1961-1973. (m) Mingat, G.; MacLellan, P.; Laars, M.; Clayden, J. Org. Lett. 2014, 16, 1252-1255.

(3)Roca, F. X.; Motevalli, M.; Richards, C. J. J. Am. Chem. Soc. 2005, 127, 2388-2389.

(4)Fischer, D. F.; Barakat, A.; Xin, Z.; Weiss, M. E.; Peters, R. Chem. Eur. J. 2009, 15, 8722-8741.

(5)Weiss, M. E.; Fischer, D. F.; Xin, Z.; Jautze, S.; Schweizer, W. B.; Peters, R. Angew. Chem. Int. Ed. 2006, 45, 5694-5698.

(6)For a review see: Nomura, H.; Richards, C. J. Chem. Asian J. 2010, 5, 1726-1740.

(7)For other planar chiral palladacycles synthesised by diastereoselective palladation see: (a) Richards, C. J. In Chiral Ferrocenes in Asymmetric Catalysis; Synthesis and Applications, Dai, L.-X.; Hou, X.-L., Eds.; Wiley-VCH: Weinheim, 2010; pp 337-368. (b) Gan, K.; Sadeer, A.; Xu, C.; Li, Y.; Pullarkat, S. A. Organometallics 2014, 33, 5074-5076.

(8)Stevens, A. M.; Richards, C. J. Organometallics 1999, 18, 1346-1348.

(9)Prasad, R. S.; Anderson, C. E.; Richards, C. J.; Overman, L. E. Organometallics 2005, 24, 77-81.

(10)Anderson, C. E.; Overman, L. E.; Richards, C. J.; Watson, M. P.; White, N. Org. Synth. 2007, 84, 139-147.

(11)Kazi, A. B.; Jones, G. D.; Vicic, D. A. Organometallics 2005, 24, 6051-6054.

(12) (a) Gorunova, O. N.; Keuseman, K. J.; Goebel, B. M.; Kataeva, N. A.; Churakov, A. V.; Kuz’mina, L. G.; Dunina, V. V.; Smoliakova, I. P. J. Organomet. Chem. 2004, 689, 2382-2394. (b) Mawo, R. Y.; Johnson, D. M.; Wood, J. L.; Smoliakova, I. P. J. Organomet. Chem. 2008, 693, 33-45.

(13)A list of structures and references is given in the supporting information.

(14)Bercaw, J. E.; Durrell, A. C.; Gray, H. B.; Green, J. C.; Hazari, N.; Labinger, J. A.; Winkler, J. R. Inorg. Chem. 2010, 49, 1801-1810.

(15)(a) Blanco, J.; Gayoso, E.; Vila, J. M.; Gayoso, M.; Maichle-Mössmer, C.; Strähle, J. Z. Naturforsch. 1993, 48b, 906-910. (b) Freiesleben, D.; Polborn, K.; Robl, C.; Sünkel, K.; Beck, W. Can. J. Chem. 1995, 73, 1164-1174. (c) Zhao, G.; Yang, Q.-C.; Mak, T. C. W. Organometallics 1999, 18, 3623-3636. (d) Mercier, A.; Wagschal, S.; Guénée, L.; Besnard, C.; Kündig, E. P. Organometallics 2013, 32, 3932-3942.

(16)The trans-configured pivalate-bridged derivative of 1a has also been reported: Olson, A. C.; Overman, L. E.; Sneddon, H. F.; Ziller, J. W. Adv. Synth. Catal. 2009, 351, 3186-3192.

(17)Panchal, K.; Amin, J.; Roca, F. X.; Motevalli, M.; Horton, P.N.; Coles S. J.; Richards, C. J. J. Organomet. Chem. 2015, 775, 12-19.

(18)Yeamine, M. R.; Richards, C. J. Tetrahedron: Asymmetry 2007, 18, 2613-2616.

(19)(a) Lafrance, M.; Rowley, C. N.; Woo, T. K.; Fagnou, K. J. Am. Chem. Soc. 2006, 128, 8754-8756. (b) García-Cuadrado, D.; de Mendoza, P.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. J. Am. Chem. Soc. 2007, 129, 6880-6886. (c) Gorelsky, S. I.; Lapointe, D.; Fagnou, K. J. Am. Chem. Soc. 2008, 130, 10848-10849.

(20)(a) Sammakia, T.; Latham, H. A.; Schaad, D. R. J. Org. Chem. 1995, 60, 10-11. (b) Richards, C. J.; Damalidis, T.; Hibbs, D. E.; Hursthouse, M. B. Synlett 1995, 74-76. (c) Nishibayashi, Y.; Uemura, S. Synlett 1995, 79-81.

(21)Xia, J.-B.; You, S.-L. Organometallics 2007, 26, 4869-4871.

(22)Garcia, M. A.; Frey. W.; Peters, R. Organometallics 2014, 33, 1068-1078.

(23)The diastereoselectivity of lithiation of a ferrocenyloxazoline and a pentaphenylferrocenyloxazoline, both derived from (S)-valine, is revered with use of bis(2-tert-butoxyethyl)ether as an additive. See reference 22 and: Herbert, S. A.; Castell, D. C.; Clayden, J.; Arnott, G. E. Org. Lett. 2013, 15, 3334-3337.

(24)Coles, S. J.; Gale, P. A. Chem. Sci. 2012, 3, 683-689.

(25)Rigaku, CrystalClear- SM Expert 3.1 b27, 2013.

(26)Sheldrick, G.M., Acta Cryst. 2015, C71, 3-8.

(S,Sp)-16a850849.5849848.5848847.5847846.5846845.5845844.5844843.5843842.5842841.5841840.5840839.5839838.5838837.5837836.5836835.5835834.5834833.5833832.5832831.5831830.5830829.5829828.5828827.5827826.5826825.5825824.5824823.5823822.5822821.5821820.5820819.5819818.5818817.5817816.5816815.5815814.5814813.5813812.5812811.5811810.5810809.5809808.5808807.5807806.5806805.5805804.5804803.5803802.5802801.5801800.5800799.5799798.5798797.5797796.5796795.5795794.5794793.5793792.5792791.5791790.5790789.5789788.5788787.5787786.5786785.5785784.5784783.5783782.5782781.5781780.5780779.5779778.5778777.5777776.5776775.5775774.5774773.5773772.5772771.5771770.5770769.5769768.5768767.5767766.5766765.5765764.5764763.5763762.5762761.5761760.5760759.5759758.5758757.5757756.5756755.5755754.5754753.5753752.5752751.5751750.5750749.5749748.5748747.5747746.5746745.5745744.5744743.5743742.5742741.5741740.5740739.5739738.5738737.5737736.5736735.5735734.5734733.5733732.5732731.5731730.5730729.5729728.5728727.5727726.5726725.5725724.5724723.5723722.5722721.5721720.5720719.5719718.5718717.5717716.5716715.5715714.5714713.5713712.5712711.5711710.5710709.5709708.5708707.5707706.5706705.5705704.5704703.5703702.5702701.5701700.5700699.5699698.5698697.5697696.5696695.5695694.5694693.5693692.5692691.5691690.5690689.5689688.5688687.5687686.5686685.5685684.5684683.5683682.5682681.5681680.5680679.5679678.5678677.5677676.5676675.5675674.5674673.5673672.5672671.5671670.5670669.5669668.5668667.5667666.5666665.5665664.5664663.5663662.5662661.5661660.5660659.5659658.5658657.5657656.5656655.5655654.5654653.5653652.5652651.5651650.5650649.5649648.5648647.5647646.5646645.5645644.5644643.5643642.5642641.5641640.5640639.5639638.5638637.5637636.5636635.5635634.5634633.5633632.5632631.5631630.5630629.5629628.5628627.5627626.5626625.5625624.5624623.5623622.5622621.5621620.5620619.5619618.5618617.5617616.5616615.5615614.5614613.5613612.5612611.5611610.5610609.5609608.5608607.5607606.5606605.5605604.5604603.5603602.5602601.5601600.5600599.5599598.5598597.5597596.5596595.5595594.5594593.5593592.5592591.5591590.5590589.5589588.5588587.5587586.5586585.5585584.5584583.5583582.5582581.5581580.5580579.5579578.5578577.5577576.5576575.5575574.5574573.5573572.5572571.5571570.5570569.5569568.5568567.5567566.5566565.5565564.5564563.5563562.5562561.5561560.5560559.5559558.5558557.5557556.5556555.5555554.5554553.5553552.5552551.5551550.5550549.5549548.5548547.5547546.5546545.5545544.5544543.5543542.5542541.5541540.5540539.5539538.5538537.5537536.5536535.5535534.5534533.5533532.5532531.5531530.5530529.5529528.5528527.5527526.5526525.5525524.5524523.5523522.5522521.5521520.5520519.5519518.5518517.5517516.5516515.5515514.5514513.5513512.5512511.5511510.5510509.5509508.5508507.5507506.5506505.5505504.5504503.5503502.5502501.5501500.5500499.5499498.5498497.5497496.5496495.5495494.5494493.5493492.5492491.5491490.5490489.5489488.5488487.5487486.5486485.5485484.5484483.5483482.5482481.5481480.5480479.5479478.5478477.5477476.5476475.5475474.5474473.5473472.5472471.5471470.5470469.5469468.5468467.5467466.5466465.5465464.5464463.5463462.5462461.5461460.5460459.5459458.5458457.5457456.5456455.5455454.5454453.5453452.5452451.5451450.5450449.5449448.5448447.5447446.5446445.5445444.5444443.5443442.5442441.5441440.5440439.5439438.5438437.5437436.5436435.5435434.5434433.5433432.5432431.5431430.5430429.5429428.5428427.5427426.5426425.5425424.5424423.5423422.5422421.5421420.5420419.5419418.5418417.5417416.5416415.5415414.5414413.5413412.5412411.5411410.5410409.5409408.5408407.5407406.5406405.5405404.5404403.5403402.5402401.5401400.5400399.5399398.5398397.5397396.5396395.5395394.5394393.5393392.5392391.5391390.5390389.5389388.5388387.5387386.5386385.5385384.5384383.5383382.5382381.5381380.5380379.5379378.5378377.5377376.5376375.5375374.5374373.5373372.5372371.5371370.5370369.5369368.5368367.5367366.5366365.5365364.5364363.5363362.5362361.5361360.5360359.5359358.5358357.5357356.5356355.5355354.5354353.5353352.5352351.5351350.5350349.5349348.5348347.5347346.5346345.5345344.5344343.5343342.5342341.5341340.5340339.5339338.5338337.5337336.5336335.5335334.5334333.5333332.5332331.5331330.5330329.5329328.5328327.5327326.5326325.5325324.5324323.5323322.5322321.5321320.5320319.5319318.5318317.5317316.5316315.5315314.5314313.5313312.5312311.5311310.5310309.5309308.5308307.5307306.5306305.5305304.5304303.5303302.5302301.5301300.5300299.5299298.5298297.5297296.5296295.5295294.5294293.5293292.5292291.5291290.5290289.5289288.5288287.5287286.5286285.5285284.5284283.5283282.5282281.5281280.5280279.5279278.5278277.5277276.5276275.5275274.5274273.5273272.5272271.5271270.5270269.5269268.5268267.5267266.5266265.5265264.5264263.5263262.5262261.5261260.5260259.5259258.5258257.5257256.5256255.5255254.5254253.5253252.5252251.5251250.5250249.5249248.5248247.5247246.5246245.5245244.5244243.5243242.5242241.5241240.5240239.5239238.5238237.5237236.5236235.5235234.5234233.5233232.5232231.5231230.5230229.5229228.5228227.5227226.5226225.5225224.5224223.5223222.5222221.5221220.5220-0.62332999999999994-0.39184890000000089-0.590656000000000290.177402000000000340.747180000000000621.08095500000000011.4686551.47843499999999821.426180.835577200000000020.18686800000000031-1.0386000000000024E-2-0.55549300000000001-1.2352209999999979-1.2592979499999999-1.0129909999999998-0.600082-0.52386900000000003-0.352718000000000312.7895999999999976E-20.136550999999999920.318533400000000020.282800600000000510.264938000000000010.305081000000000320.293814400000000759.8688000000000178E-2-6.2418000000000133E-2-0.25315600000000005-0.129329999999999950.222980000000000150.45361100000000010.407761000000000040.615158000000000650.963126000000000041.16698863000000011.00973429999999630.935679999999999851.08567200000000021.1778831.1353131.12485530000000011.17300800000000011.1957051.04816699999999980.764868999999999910.809055999999999890.716160999999999490.641261000000000640.412668000000000310.431813000000000560.585517999999998320.700797000000001110.745671000000001530.766980000000000990.764170999999999930.714930999999999980.654294000000001260.567716000000000110.592723000000000440.533823000000000050.505529000000000010.646505999999999910.708111900000000020.736051000000001010.735370000000000630.662344000000001150.601685000000001140.468820700000000650.407327200000000440.388046370000000640.4211490.536649000000001150.42850040000000050.489443748999999980.420123300000000310.225342100000000248.9773600000000023E-21.1862000000000043E-2-0.14716199999999996-4.4586000000000119E-2-3.5867000000000072E-25.1470000000000016E-20.178656000000000040.245131999999999960.359079000000000310.582375999999999560.64177800000000140.794226199999999110.958184999999999511.05352799999999981.01513689999999790.984827100000000070.740649400000002010.573309999999999990.531293000000000020.394543000000000310.28914500000000010.329157000000000310.371628000000000570.450900000000000080.549601999999999920.513937000000000090.525314999999998980.491773000000000070.582128999999999560.571428999999999960.505986999999998850.444376000000000660.486648000000000080.533032000000000060.537179000000000630.364422000000000580.419330000000000310.607461000000000030.700865999999999990.757242000000000640.741946000000000880.745291000000001150.791552999999998730.728943000000001010.662601000000001770.568524000000000030.535595999999999960.562695500000001010.629080199999999980.690393100000000310.662820000000001410.665146000000001010.599346999999999190.610299000000001150.612592000000000030.627218999999999970.594885999999999580.614438000000000040.66999900000000190.681369099999999510.600802999999999980.478382000000000640.356382000000000640.263595000000000020.191278000000000140.11929900000000020.212094000000000280.324042000000000440.482966000000000510.602685000000001140.754251200000001010.789565699999999590.79028609999999910.736157999999999980.752429000000001010.623064999999999980.564993000000000630.581139999999999430.572646999999999910.526725000000000890.644280999999999990.616858000000001020.663783000000001010.677500000000000880.729144000000001010.758537000000000130.791361999999999570.687394000000000840.697635000000001340.703203000000000020.671911000000001150.728982000000000020.728501000000000620.766056000000000630.786492000000000080.801436999999998840.751700000000001030.632233000000000040.425279000000000070.281983000000000320.201828000000000010.161319000000000247.6364000000000098E-22.6910000000000007E-24.742700000000008E-20.109365999999999960.194190000000000110.185941000000000380.224762000000000240.232263000000000220.268042000000000060.340613000000000220.367395000000000080.388678000000000580.445972000000000370.469971000000000080.521851000000000620.559493999999999490.585758000000000330.6021360.576815000000000630.5198760.502505999999999560.5066560.488389000000000570.476892000000000320.4776550.441031000000000010.478479000000000320.50010999999999950.487619000000000020.428116000000000440.388644000000000320.406232000000000040.369220000000000380.335242000000000320.360425000000000380.377341000000000320.399265000000000310.411869000000000320.434516000000000510.480102000000000080.446592000000000210.38100000000000050.330029000000000630.329944000000000570.322732000000000020.310916000000000640.327329000000000870.362354000000000560.419631000000000030.540057000000000010.634179000000001160.7105920.729354999999999980.661145000000001650.692572000000000410.656822999999999930.55770299999999950.534222000000000090.487778000000000320.479361000000000310.486527000000000320.536187000000000080.554842999999999980.526696000000000050.485192000000000010.4640590.427664000000000320.403067000000000010.343787000000000180.34559100000000020.32804600000000050.323657000000000080.3501010.377899000000000320.376423000000000560.355084000000000510.366810000000000580.414783000000000070.403147000000000030.429708000000000310.428726000000000380.351098000000000020.393863000000000630.370190000000000070.368417000000000380.403253000000000030.346939000000000220.348217000000000220.429376000000000760.430734000000000060.431350000000000570.393539000000000080.296848000000000440.299914000000000510.318149000000000020.267014000000000080.243985000000000280.239841000000000220.327176000000000580.434949000000000310.499401000000000320.53248899999999910.578033999999999490.607676000000000880.612493999999999980.574243000000000610.564101999999999990.548453199999998970.48941940000000050.433795000000000040.41696200000000050.405298000000000050.436465000000000320.394174000000000580.402276000000000020.402572000000000320.41882300000000050.40970500000000010.425677000000000080.390072000000000640.372439000000000080.340753000000000030.334836000000000580.332223000000000320.341223000000000220.328912000000000870.334369000000000750.412933800000000020.448651099999999970.424844100000000450.419678000000000380.355075000000000080.336664000000000570.321182000000000580.292029000000000320.329123000000000440.373764000000000320.428128000000000510.442858900000000610.450836400000000080.424841000000000080.369168000000000380.326059000000000320.277155000000000040.26655900000000010.297894000000000380.271838000000000020.260520000000000080.296481000000000380.349484000000000740.364233000000000030.381744100000000310.420226700000000510.397943300000000440.400427400000000320.360357300000000320.321506200000000570.286676400000000440.309100500000000440.345334200000000420.421578900000000760.485775700000000310.511999499999999940.499042200000000320.482275500000000020.420763800000000020.392443500000000440.389178130000000510.350680100000000380.336642900000000580.326913500000000580.354888600000000890.352289000000000020.329199000000000020.302612000000000380.307525000000000380.313943000000000080.318552000000000450.322378300000001010.284747100000000030.289392100000000320.286099700000000010.310888800000001020.353451200000000020.377429600000000640.384347000000000380.402212700000000310.416040000000000020.370593000000000060.328021000000000510.323688000000000640.288529000000000310.302658000000000320.308655000000000010.347818000000000740.407306000000000450.448696999999999960.507824999999999970.498822000000000880.476523000000000310.442401000000000210.376428000000000760.357455000000000020.371854000000000570.348010000000000490.390448000000000570.41343100000000010.463305000000000080.485794000000000060.443032999999999950.393356000000000870.322116000000000510.305508000000000450.304642000000000020.296685000000000310.322043000000000080.343973000000000420.35957400000000050.426388000000000880.439441000000000080.442282000000000170.456686000000000310.453589000000000020.437433000000000020.454096000000000060.411060000000000310.3978759000000010.336843800000000750.313812300000000880.278766100000000020.290771900000000080.301999300000000080.308481300000000510.335158900000000760.320913700000000580.316449000000000310.333138800000000510.285802800000000580.263055800000000010.229413100000000310.212365799999999990.231213200000000290.264693799999999980.279470900000000580.330765010000000080.351745600000000050.325763400000000310.346673700000000310.321405000000000380.275653362299999980.200522029999999880.123828500000000028.9639300000000199E-27.0914000000000074E-24.2358000000000041E-28.0493000000000009E-27.7920000000000059E-20.112369000000000010.149172999999999970.172194999999999990.189490000000000440.186655000000000040.169019000000000360.146008000000000250.16937000000000010.178101000000000010.179559000000000220.223492500000000150.267257499999999980.278249700000000040.27740470000000050.260735999999999970.282436900000000320.297079100000000320.259900000000000020.219116000000000280.229557000000000210.283365000000000310.261282000000000010.258906000000000080.239581999999999990.271728000000000080.337728400000000760.302301000000000320.272295999999999980.264527000000000070.250607000000000020.249874999999999990.203692999999999990.158869000000000320.158218000000000440.163864000000000150.163242000000000330.148084000000000240.157748000000000420.176159000000000010.199356000000000090.203568000000000250.175967000000000320.225918000000000370.226313000000000180.192221000000000110.209751000000000240.183499000000000410.157779000000000250.179960000000000290.155524000000000220.132826999999999978.9907000000000098E-23.2630000000000124E-25.7649999999999979E-20.11368400000000010.122122000000000190.116610999999999950.156397000000000260.223737000000000240.234072999999999980.203467000000000290.138373000000000020.106667999999999990.113705000000000159.092700000000016E-23.6982000000000056E-22.0166000000000007E-23.7876000000000042E-22.1280000000000056E-2-2.1328000000000007E-2-2.8777999999999995E-2-2.2739000000000068E-24.7406000000000101E-28.9112000000000025E-29.5630000000000104E-20.104254000000000120.103638000000000027.8763000000000111E-27.1964000000000097E-26.6133999999999984E-27.9736000000000126E-20.117483000000000060.132221000000000030.16325400000000020.147117000000000190.121643000000000145.1635999999999987E-2-2.0841000000000002E-2-3.3096E-2-2.4005000000000016E-21.7929000000000021E-24.8697000000000025E-26.7090000000000052E-20.140023999999999980.186285000000000280.201785000000000210.169943000000000430.149890000000000250.152225000000000250.151600000000000010.139056000000000010.107644999999999990.132037999999999990.141878999999999989.6802000000000027E-24.9695000000000031E-22.4497000000000081E-21.8089999999999995E-2-4.1410000000000101E-3-9.9300000000000568E-3-8.7860000000000247E-35.2429999999999994E-33.5699999999999691E-4-2.3662999999999983E-2-5.4462000000000149E-2-5.1088999999999996E-2-7.2186000000000139E-2-2.0555999999999991E-2-1.4459E-2-3.4180000000000356E-31.832499999999998E-25.7388000000000099E-25.4004000000000066E-25.0455000000000062E-22.2232000000000085E-24.6218999999999996E-27.0736000000000146E-28.0487000000000031E-20.107593000000000220.143402000000000220.140575999999999980.118476000000000150.120529000000000090.105063000000000140.124929999999999990.140374999999999978.1024000000000179E-20.104520000000000110.100823000000000027.4881000000000086E-26.6290000000000029E-2-1.4322000000000001E-2-1.9262000000000026E-2-2.4529999999999993E-2-4.0270999999999987E-2-1.5529999999999717E-3-3.4610000000000495E-3-2.733500000000005E-21.262800000000004E-22.6239000000000064E-24.1217000000000004E-25.8267000000000034E-23.456999999999999E-25.4593000000000121E-27.506700000000012E-26.2991000000000089E-25.237700000000009E-26.9455000000000114E-26.499700000000011E-25.0382000000000149E-22.3189999999999988E-23.2337000000000039E-24.4543000000000034E-24.1405999999999998E-24.9853000000000133E-24.7385000000000045E-27.9581000000000068E-29.5328000000000065E-28.7396000000000043E-24.1665999999999967E-2-1.5498999999999978E-2-3.4899000000000069E-2-3.8756999999999986E-2-2.3824999999999978E-2-2.2052000000000009E-2-2.6302999999999983E-21.5881000000000055E-24.2177999999999993E-27.0483000000000059E-29.9036000000000179E-27.0932000000000009E-20.109079000000000060.123916999999999940.111105000000000128.6209000000000036E-24.3784000000000017E-23.6273000000000069E-27.9650000000000103E-3-2.5814000000000021E-2-1.9637999999999933E-2-5.1299999999999714E-3-1.8908999999999961E-2-2.0267000000000042E-2-5.5951000000000084E-2-6.0424000000000033E-2-7.7673000000000034E-2-8.5718000000000044E-2-5.333500000000007E-2-5.2518000000000065E-2-5.0265000000000004E-2-5.5109000000000026E-2-6.0149999999999967E-2-5.675700000000012E-2-7.8451999999999994E-2-9.5938000000000204E-2-9.0231000000000061E-2-8.627300000000003E-2-7.4496000000000173E-2-7.6233000000000023E-2-0.10127200000000014-8.6933000000000038E-2-5.633900000000009E-2-5.3473000000000014E-2-3.7944999999999895E-2-4.3894000000000044E-2-4.1341999999999976E-2-2.0242999999999921E-2-1.6513000000000014E-2-2.6844000000000028E-2-1.7749000000000036E-2-6.7041000000000031E-2-6.7920000000000022E-2-7.9471000000000055E-2-0.12248300000000002-0.1110379999999999-0.13053599999999999-0.16325900000000024-0.14202800000000004-0.13176900000000025-9.2779000000000056E-2-5.6252999999999997E-2-8.3002000000000048E-2-5.7361000000000099E-2-6.4517000000000088E-2-7.3438000000000073E-2-8.4387000000000018E-2-0.12433499999999997-0.14155300000000004-0.17765799999999998-0.15747800000000028-9.4999000000000208E-2-8.575100000000016E-2-3.7328999999999946E-2-3.4002000000000115E-2-7.281800000000016E-2-3.3050999999999942E-21.049100000000004E-2-5.8679999999999869E-3-7.7249000000000012E-2-0.14506500000000025-0.12938799999999995-9.4074000000000199E-2-0.15485800000000027-0.22361100000000009-0.23353599999999999-0.20147099999999996-0.20597000000000001-0.24130300000000021-0.26960900000000004-0.23884500000000033-0.234352-0.25441200000000008-0.28870600000000002-0.28079100000000001-0.30042700000000044-0.30369600000000008-0.34595900000000029-0.34719200000000017-0.34253800000000018-0.32435000000000075-0.32778600000000058-0.31545600000000062-0.32872300000000032-0.35962700000000031-0.38049400000000044-0.38442300000000063-0.40773999999999988-0.37759400000000032-0.37812200000000051-0.36451500000000031-0.35071700000000006-0.34948700000000066-0.35119500000000015-0.36498200000000075-0.39740200000000075-0.43031100000000055-0.39075000000000032-0.3687410000000001-0.38505500000000031-0.40008800000000044-0.45343800000000001-0.4747340000000001-0.48476300000000005-0.49847700000000056-0.49809100000000006-0.43832900000000063-0.41822800000000032-0.32922100000000032-0.32998300000000064-0.34598700000000049-0.35416800000000032-0.39884000000000064-0.45937800000000056-0.48715700000000006-0.51963799999999949-0.71617700000000062-0.64825100000000102-0.60500500000000101-0.54652100000000003-0.538381-0.55148299999999872-0.55753199999999958-0.51418399999999898-0.5027159999999995-0.53302000000000005-0.62583300000000064-0.69395699999999949-0.64438499999999999-0.62353199999999998-0.64724500000000162-0.67178200000000077-0.6920900000000012-0.63853300000000002-0.64535299999999951-0.7153520000000001-0.75427400000000111-0.78438800000000009-0.83371399999999996-0.87886000000000064-0.94239300000000004-0.93737299999999957-0.91834500000000063-0.94147799999999959-0.92696599999999996-0.8668769999999999-0.78374300000000063-0.72101999999999999-0.70122099999999998-0.71775600000000062-0.68924200000000024-0.728155000000001-0.8000659999999995-0.8605330000000001-0.89645700000000039-0.93978200000000012-0.97056799999999888-1.045347-1.0241899999999999-1.0000550000000001-0.96872200000000064-0.93795799999999951-0.91596900000000003-0.82561000000000062-0.75858299999999956-0.75650500000000065-0.7759610000000009-0.83131600000000017-0.89929500000000073-0.88833599999999957-0.96390200000000004-0.99102599999999996-1.0445180000000001-1.116376-1.1059279999999998-1.0797689999999998-1.1333059999999999-1.109256-1.1421890000000001-1.0882799999999999-1.0459499999999982-1.0698189999999999-1.0612819-1.0498651999999984-1.0415809999999999-1.0509299999999984-1.0432049999999982-1.0657369999999982-1.090835-1.1233460000000002-1.1217965999999981-1.1083510000000001-1.1198532999999982-1.1493936999999979-1.1729586000000001-1.2189894999999982-1.2687609-1.3280965999999998-1.3500750000000001-1.3482419999999999-1.33026-1.2941570000000022-1.2705379999999999-1.270675-1.2851699999999981-1.3031809999999999-1.3338109999999999-1.373985-1.392468-1.4605909999999998-1.4644599999999999-1.4756269999999974-1.4616079999999998-1.4353529999999999-1.472132-1.4947400000000002-1.486065-1.5057459999999998-1.5018799999999977-1.5379639999999979-1.5695709999999998-1.5178279999999984-1.4994629999999998-1.5270899999999998-1.607108-1.7329039999999998-1.7908810000000008-1.8667639999999999-2.0086049999999998-2.0751200000000001-2.168120000000004-2.220310000000004-2.26206-2.3370599999999961-2.4037600000000001-2.4736099999999968-2.5303100000000001-2.53789-2.5421300000000002-2.53938-2.5130449999999978-2.540219-2.5331070000000002-2.5522389999999966-2.573086-2.6252070000000001-2.6943199999999998-2.7646000000000002-2.8508199999999961-2.9079299999999999-2.9956199999999966-3.1015999999999995-3.1521699999999977-3.2038799999999998-3.22424-3.2576900000000002-3.3147999999999977-3.3213600000000003-3.351669999999995-3.3986599999999947-3.4607200000000002-3.491869999999996-3.5008499999999967-3.52989-3.5507800000000005-3.54297-3.5426799999999967-3.5202999999999998-3.5474900000000011-3.5803569999999998-3.6257600000000001-3.6606840000000012-3.6771960000000012-3.7411790000000011-3.8221689999999966-3.870984-3.8783600000000003-3.9260349999999997-3.9964519999999957-4.0529499999999965-4.0614360000000005-4.0775600000000001-4.1046610000000001-4.1153849999999865-4.1511099999999965-4.1608129999999885-4.1689899999999884-4.2240660000000005-4.2360670000000091-4.2397420000000112-4.259322000000008-4.2837100000000001-4.2861490000000071-4.3100490000000002-4.3100309999999933-4.3316230000000102-4.4092520000000084-4.4601920000000002-4.4965659999999996-4.5400589999999985-4.5928119999999932-4.6413700000000002-4.6320539999999975-4.6149409999999884-4.5944789999999927-4.5889859999999913-4.5593519999999996-4.5766940000000034-4.6608689999999955-4.7154039999999995-4.7048569999999916-4.7565770000000001-4.8035010000000007-4.7540510000000005-4.6947799999999926-4.6801630000000003-4.6976900000000006-4.7231869999999914-4.6983839999999955-4.7792450000000093-4.8663139999999965-4.9417490000000122-5.0155449999999933-5.1298879999999913-5.2098380000000004-5.3151259999999914-5.3739629999999998-5.4498730000000082-5.528683-5.6102910000000001-5.6758980000000001-5.793501-5.8484220000000002-5.9459870000000006-6.1098410000000003-6.2435289999999997-6.3597229999999998-6.5291920000000001-6.704339-6.9189749999999917-7.1131549999999866-7.245018-7.4059400000000002-7.5861859999999917-7.7792430000000152-7.9670519999999945-8.1729700000000012-8.409967-8.6310669999999998-8.8500960000000166-9.0976300000000005-9.3421030000000016-9.5916709999999998-9.8091950000000008-9.9745070000000027-10.194065-10.382720000000004-10.583067-10.747571999999998-10.9377-11.182397-11.450686000000024-11.671417-11.900725-12.057648-12.211846-12.344997000000001-12.460139000000018-12.549737-12.614351999999998-12.648926999999997-12.738511999999998-12.815962000000004-12.872288000000006-12.944123999999999-13.009217-13.188477000000001-13.303024000000002-13.366312000000002-13.441591000000001-13.462678000000002-13.477308000000001-13.453446000000026-13.392951-13.324669-13.295852-13.279401-13.267723-13.236427000000001-13.220414000000002-13.141147999999999-13.067478000000001-12.984770000000001-12.894184000000006-12.835647000000014-12.763961-12.735354000000001-12.725858000000001-12.682102-12.671333000000001-12.629383000000001-12.598888000000001-12.545518-12.528675999999999-12.516553-12.513096000000004-12.477500000000004-12.431462-12.411861-12.411935-12.396531000000014-12.407820000000001-12.473280000000004-12.532091000000001-12.536997-12.548287-12.569302-12.574887000000002-12.534736000000002-12.510759-12.506327000000001-12.540150000000001-12.525690000000004-12.482801000000002-12.49652-12.549558000000001-12.558651000000001-12.614703-12.655443000000016-12.680544000000006-12.739579000000001-12.812398-12.889296000000016-12.975339000000016-13.020293000000001-13.051084000000015-13.123247000000001-13.117863-13.078759000000002-13.001338000000001-12.908733-12.819924-12.760426000000002-12.667278999999999-12.612144000000002-12.540525000000001-12.480899000000004-12.423641-12.313782000000014-12.217003-12.100444000000014-11.95402-11.775072-11.53576-11.272063000000001-10.995267-10.679515000000002-10.355714000000024-10.001825-9.5817259999999997-9.2135219999999993-8.8721210000000035-8.4832840000000047-8.0599720000000001-7.6051039999999945-7.1262739999999996-6.6166539999999996-6.0815760000000001-5.5375639999999997-4.9256960000000003-4.3867580000000004-3.7946039999999988-3.2366189999999957-2.6742970000000001-2.0971860000000002-1.542977-1.0477599999999998-0.491523000000000321.7365000000000096E-20.6000510000000011.1433561.69755100000000032.28380799999999962.81292099999999673.31437599999999673.82985299999999554.28651600000000074.75601599999999455.18921200000000045.60408099999998836.04956799999999986.4488746.7356970000000087.05652899999999857.32966799999999997.60281299999999327.83981099999999658.05051200000000488.26607800000000038.50452600000000038.71358400000000278.89969000000000689.06471900000000029.23988700000000139.3748460000000149.43094200000000179.47329900000000089.51598000000000089.56165600000000289.5441419999999999.56754100000000039.58792099999999979.6163849.55079500000000089.37694700000000489.24796799999999499.07791700000000118.83501800000000168.62970500000000138.42393900000000078.23727199999999198.02729300000000027.86291699999998627.71605299999999967.50883399999999857.15365999999999956.80923299999999996.56248999999999336.30462499999999265.98579800000000715.76850800000000065.69805800000000055.67003499999999335.50505099999999555.30754499999999135.11088199999999044.86402799999998964.53571800000000014.17715799999999333.91024199999999673.7064993.55009599999999773.41859999999999883.34122699999999773.30403199999999993.17966299999999613.05927699999999672.94584599999999552.77670299999999772.64757800000000022.50415100000000022.35135499999999682.20964599999999672.13077399999999971.9416731.8162731.75143780000000081.71761639999999891.71478659999999981.77809280000000051.85847032.02495682.09271249999999622.10200159999999992.12141799999999982.2438970000000042.36378699999999992.55133199999999992.84399299999999983.34923199999999983.69557400000000014.11297799999998854.54798099999998854.99914300000000815.43393600000000015.76355599999999156.20140000000000146.72939029999999957.26369189999999957.81326409999999968.2970918.8454470000000169.40353900000001819.954370000000000810.54756000000000111.07899211.58682300000000112.08556200000001412.52496312.93043400000001613.20939899999999913.46095700000000213.72361700000000113.91502314.08505600000001414.22802799999999714.33317199999999914.37366900000001414.3396714.22964800000000114.20464000000000114.07820000000000113.8276513.4902413.1820512.91945000000001512.6026212.22481999999999911.84775000000000111.51495000000000111.0832310.5578910.0728500000000049.58445000000000049.0796800000000148.44454000000000357.82877999999999657.31510999999999456.73012999999999995.994655.37035000000000024.89049999999999854.40565999999999923.93540999999999613.41461699999999673.01237199999999872.54481499999999981.84524499999999981.22689999999999770.60440000000000005-0.16710000000000011-0.92419999999999991-1.5846399999999998-2.2574500000000004-2.5478199999999998-2.8898099999999967S-CH2Cy-COP850849.5849848.5848847.5847846.5846845.5845844.5844843.5843842.5842841.5841840.5840839.5839838.5838837.5837836.5836835.5835834.5834833.5833832.5832831.5831830.5830829.5829828.5828827.5827826.5826825.5825824.5824823.5823822.5822821.5821820.5820819.5819818.5818817.5817816.5816815.5815814.5814813.5813812.5812811.5811810.5810809.5809808.5808807.5807806.5806805.5805804.5804803.5803802.5802801.5801800.5800799.5799798.5798797.5797796.5796795.5795794.5794793.5793792.5792791.5791790.5790789.5789788.5788787.5787786.5786785.5785784.5784783.5783782.5782781.5781780.5780779.5779778.5778777.5777776.5776775.5775774.5774773.5773772.5772771.5771770.5770769.5769768.5768767.5767766.5766765.5765764.5764763.5763762.5762761.5761760.5760759.5759758.5758757.5757756.5756755.5755754.5754753.5753752.5752751.5751750.5750749.5749748.5748747.5747746.5746745.5745744.5744743.5743742.5742741.5741740.5740739.5739738.5738737.5737736.5736735.5735734.5734733.5733732.5732731.5731730.5730729.5729728.5728727.5727726.5726725.5725724.5724723.5723722.5722721.5721720.5720719.5719718.5718717.5717716.5716715.5715714.5714713.5713712.5712711.5711710.5710709.5709708.5708707.5707706.5706705.5705704.5704703.5703702.5702701.5701700.5700699.5699698.5698697.5697696.5696695.5695694.5694693.5693692.5692691.5691690.5690689.5689688.5688687.5687686.5686685.5685684.5684683.5683682.5682681.5681680.5680679.5679678.5678677.5677676.5676675.5675674.5674673.5673672.5672671.5671670.5670669.5669668.5668667.5667666.5666665.5665664.5664663.5663662.5662661.5661660.5660659.5659658.5658657.5657656.5656655.5655654.5654653.5653652.5652651.5651650.5650649.5649648.5648647.5647646.5646645.5645644.5644643.5643642.5642641.5641640.5640639.5639638.5638637.5637636.5636635.5635634.5634633.5633632.5632631.5631630.5630629.5629628.5628627.5627626.5626625.5625624.5624623.5623622.5622621.5621620.5620619.5619618.5618617.5617616.5616615.5615614.5614613.5613612.5612611.5611610.5610609.5609608.5608607.5607606.5606605.5605604.5604603.5603602.5602601.5601600.5600599.5599598.5598597.5597596.5596595.5595594.5594593.5593592.5592591.5591590.5590589.5589588.5588587.5587586.5586585.5585584.5584583.5583582.5582581.5581580.5580579.5579578.5578577.5577576.5576575.5575574.5574573.5573572.5572571.5571570.5570569.5569568.5568567.5567566.5566565.5565564.5564563.5563562.5562561.5561560.5560559.5559558.5558557.5557556.5556555.5555554.5554553.5553552.5552551.5551550.5550549.5549548.5548547.5547546.5546545.5545544.5544543.5543542.5542541.5541540.5540539.5539538.5538537.5537536.5536535.5535534.5534533.5533532.5532531.5531530.5530529.5529528.5528527.5527526.5526525.5525524.5524523.5523522.5522521.5521520.5520519.5519518.5518517.5517516.5516515.5515514.5514513.5513512.5512511.5511510.5510509.5509508.5508507.5507506.5506505.5505504.5504503.5503502.5502501.5501500.5500499.5499498.5498497.5497496.5496495.5495494.5494493.5493492.5492491.5491490.5490489.5489488.5488487.5487486.5486485.5485484.5484483.5483482.5482481.5481480.5480479.5479478.5478477.5477476.5476475.5475474.5474473.5473472.5472471.5471470.5470469.5469468.5468467.5467466.5466465.5465464.5464463.5463462.5462461.5461460.5460459.5459458.5458457.5457456.5456455.5455454.5454453.5453452.5452451.5451450.5450449.5449448.5448447.5447446.5446445.5445444.5444443.5443442.5442441.5441440.5440439.5439438.5438437.5437436.5436435.5435434.5434433.5433432.5432431.5431430.5430429.5429428.5428427.5427426.5426425.5425424.5424423.5423422.5422421.5421420.5420419.5419418.5418417.5417416.5416415.5415414.5414413.5413412.5412411.5411410.5410409.5409408.5408407.5407406.5406405.5405404.5404403.5403402.5402401.5401400.5400399.5399398.5398397.5397396.5396395.5395394.5394393.5393392.5392391.5391390.5390389.5389388.5388387.5387386.5386385.5385384.5384383.5383382.5382381.5381380.5380379.5379378.5378377.5377376.5376375.5375374.5374373.5373372.5372371.5371370.5370369.5369368.5368367.5367366.5366365.5365364.5364363.5363362.5362361.5361360.5360359.5359358.5358357.5357356.5356355.5355354.5354353.5353352.5352351.5351350.5350349.5349348.5348347.5347346.5346345.5345344.5344343.5343342.5342341.5341340.5340339.5339338.5338337.5337336.5336335.5335334.5334333.5333332.5332331.5331330.5330329.5329328.5328327.5327326.5326325.5325324.5324323.5323322.5322321.5321320.5320319.5319318.5318317.5317316.5316315.5315314.5314313.5313312.5312311.5311310.5310309.5309308.5308307.5307306.5306305.5305304.5304303.5303302.5302301.5301300.5300299.5299298.5298297.5297296.5296295.5295294.5294293.5293292.5292291.5291290.5290289.5289288.5288287.5287286.5286285.5285284.5284283.5283282.5282281.5281280.5280279.5279278.5278277.5277276.5276275.5275274.5274273.5273272.5272271.5271270.5270269.5269268.5268267.5267266.5266265.5265264.5264263.5263262.5262261.5261260.5260259.5259258.5258257.5257256.5256255.5255254.5254253.5253252.5252251.5251250.5250249.5249248.5248247.5247246.5246245.5245244.5244243.5243242.5242241.5241240.5240239.5239238.5238237.5237236.5236235.5235234.5234233.5233232.5232231.5231230.5230229.5229228.5228227.5227226.5226225.5225224.5224223.5223222.5222221.5221220.52200.781055000000000050.516626000000000030.603249999999999950.88263499999999950.8397000000000010.32383100000000031-0.16054100000000018-0.59278900000000034-0.20158100000000001-1.3159199999999999E-2-2.705990000000006E-27.1026600000000079E-20.209515000000000280.34453100000000020.5685270.897678000000000750.724612000000000030.721655000000001160.924795999999999951.11766999999999821.162960.804406999999998980.565454000000000010.453140000000000040.288004000000000320.385095000000000020.246341000000000280.274017000000000010.120955999999999987.7331500000000108E-29.0994300000000222E-20.11835000000000001-0.17673000000000022-0.29687500000000044-0.21301300000000029-5.5200199999999977E-2-0.10052800000000002-2.3025499999999987E-2-2.37488E-2-3.8266000000000001E-2-2.212830000000001E-2-7.7539100000000014E-2-1.47522E-2-9.1857900000000259E-4-0.128354-4.4409200000000044E-2-0.131189-0.24681100000000025-0.37708700000000051-0.68250400000000033-0.82319299999999951-0.8937349999999995-0.94928599999999996-0.86436500000000005-0.91278400000000004-0.93691999999999998-0.93280300000000005-0.94579800000000114-0.94739399999999996-0.95909100000000114-1.0288999999999981-1.0004299999999982-0.90593900000000005-0.74713399999999996-0.64020100000000102-0.50343899999999897-0.44870899999999997-0.36873800000000001-0.3477570000000002-0.37176500000000001-0.38833300000000032-0.47573200000000004-0.45955800000000002-0.28006300000000001-0.137604-3.4838900000000061E-2-9.939580000000026E-33.7985200000000059E-20.10603000000000011-8.6721800000000182E-2-0.24684400000000029-0.32943700000000031-0.43188500000000057-0.503-0.53693199999999996-0.473553-0.43347200000000058-0.2550110000000001-0.20842300000000022-8.897400000000022E-2-1.1025999999999999E-2-9.8165900000000222E-2-0.20352200000000001-0.4419490000000002-0.65885900000000153-0.79146699999999859-0.95940899999999996-0.99870899999999996-0.93476599999999999-0.718835000000001-0.5154509999999991-0.45625600000000005-0.361703-0.23072500000000001-0.18183299999999999-0.258853-0.39402200000000076-0.50078999999999996-0.43150000000000038-0.46511200000000008-0.4782010000000001-0.51925699999999897-0.45768700000000001-0.39566700000000032-0.37313200000000002-0.47787200000000057-0.51764200000000005-0.64558099999999996-0.66164200000000128-0.65637500000000115-0.59744599999999959-0.49746400000000057-0.38544900000000032-0.37616600000000044-0.32280600000000076-0.37009900000000001-0.46696500000000002-0.57688899999999999-0.68668800000000074-0.74423799999999996-0.77327600000000052-0.78773199999999999-0.80346099999999898-0.70184899999999995-0.57124900000000101-0.47057200000000032-0.44830300000000017-0.31878100000000031-0.17639500000000022-0.10769700000000011-0.15127299999999999-0.262762-0.231659-0.23270600000000022-0.2772190000000001-0.38271200000000044-0.42775300000000011-0.36898500000000051-0.38338900000000076-0.41278100000000001-0.5061129999999987-0.48844600000000032-0.37601300000000032-0.36591800000000058-0.45088800000000051-0.50795900000000005-0.57014500000000101-0.59339299999999906-0.6885800000000003-0.76840799999999998-0.79606900000000003-0.72471300000000005-0.66407500000000153-0.61197500000000116-0.55639000000000005-0.53651699999999858-0.57191499999999951-0.62108799999999997-0.67109400000000152-0.72576000000000063-0.79782399999999998-0.88538199999999956-0.89458599999999944-0.89474800000000088-0.90170899999999998-0.85546900000000003-0.78601100000000002-0.67127400000000115-0.61505699999999996-0.53894299999999951-0.45455300000000004-0.40518500000000002-0.37071500000000002-0.37072400000000044-0.3550930000000001-0.3568270000000005-0.36030300000000032-0.38199500000000008-0.38921200000000045-0.43240700000000032-0.49113800000000002-0.50221599999999911-0.48931600000000064-0.50072300000000003-0.5096619999999995-0.49668600000000057-0.50004300000000002-0.43507400000000057-0.4452730000000002-0.466617-0.48308100000000032-0.51157799999999898-0.57309299999999996-0.59155899999999906-0.63400299999999998-0.62747200000000003-0.65424800000000116-0.66389500000000201-0.66175200000000101-0.62990100000000115-0.64209000000000116-0.67056000000000004-0.645706000000001-0.57325400000000004-0.51086699999999885-0.50757099999999911-0.46725800000000001-0.43536100000000044-0.42536900000000044-0.43453700000000001-0.51891500000000002-0.58324299999999918-0.60151100000000002-0.63570200000000088-0.64825100000000102-0.66093700000000088-0.68131699999999906-0.59630999999999956-0.54554100000000005-0.52821399999999885-0.54179999999999995-0.52990099999999996-0.545825000000001-0.57250100000000004-0.62153899999999951-0.63752399999999998-0.64244100000000115-0.6929260000000006-0.69331399999999932-0.66551499999999997-0.65165100000000165-0.66406900000000102-0.648563-0.62402299999999999-0.58274200000000032-0.56874400000000114-0.522424-0.47311700000000001-0.44757400000000042-0.4290680000000005-0.45181900000000008-0.42829300000000003-0.46666000000000002-0.44791300000000017-0.46726400000000001-0.45835300000000001-0.45476100000000003-0.43136600000000075-0.41287200000000057-0.39651500000000051-0.43576700000000002-0.46298800000000051-0.46042500000000008-0.47706900000000002-0.478653-0.49768400000000057-0.52477099999999999-0.50513299999999883-0.46521000000000001-0.43803700000000001-0.45998500000000031-0.49491300000000032-0.52113599999999949-0.48179300000000003-0.50277400000000005-0.55233500000000002-0.56992799999999999-0.56544499999999998-0.502139-0.46629900000000002-0.48175000000000001-0.48402100000000031-0.48087800000000075-0.46162400000000031-0.41320800000000002-0.389297-0.34079299999999996-0.26548500000000008-0.22382500000000008-0.18533600000000025-0.17628800000000025-0.19865700000000008-0.23179000000000022-0.29367700000000002-0.34772000000000031-0.34734500000000029-0.33271800000000051-0.31371200000000032-0.30325000000000002-0.29825400000000002-0.33681300000000075-0.373145-0.37434100000000031-0.39355800000000057-0.430093-0.46004600000000001-0.42694700000000002-0.408279-0.38675800000000032-0.39216600000000057-0.38976400000000044-0.37690700000000038-0.33607200000000076-0.3475310000000002-0.34744900000000017-0.37931200000000076-0.4091550000000001-0.39342000000000088-0.36258500000000032-0.37181100000000045-0.33443600000000051-0.31294300000000008-0.26796900000000001-0.27577800000000002-0.30335100000000031-0.30437600000000065-0.29071000000000002-0.26532600000000051-0.25570400000000004-0.23834500000000025-0.231326-0.25973799999999997-0.24640800000000038-0.27981600000000051-0.30901200000000051-0.32705400000000051-0.30964700000000001-0.25072900000000004-0.20844100000000032-0.20899000000000029-0.18941600000000047-0.16768200000000008-0.16765400000000008-0.14948400000000028-0.16805100000000009-0.16268900000000008-0.15214800000000028-0.18150000000000022-0.14872400000000022-0.14590100000000025-0.14592600000000025-0.14745200000000025-0.18534500000000032-0.18910199999999999-0.20635700000000001-0.21155099999999999-0.20172999999999999-0.18718599999999999-0.142676-0.133188-9.1967800000000127E-2-6.0351600000000082E-2-6.9018600000000138E-2-0.100339-0.11249700000000004-0.12598899999999999-0.12982199999999997-0.19133600000000009-0.19691500000000037-0.139157-0.104459-0.10715000000000002-0.10809000000000014-9.5660400000000201E-2-5.3598000000000035E-2-6.625979999999998E-2-9.4866900000000198E-2-9.8062100000000166E-2-6.0012800000000109E-2-3.7246700000000056E-2-3.7231400000000093E-31.29059E-23.1738300000000039E-24.4079600000000024E-25.0167800000000033E-23.1143200000000055E-21.8096900000000007E-3-1.0617100000000001E-21.0919199999999999E-26.7272900000000024E-25.568240000000009E-25.6192000000000082E-25.5444300000000002E-26.9497700000000134E-28.4033200000000002E-25.8254999999999987E-24.4708300000000081E-32.7246100000000044E-23.3001700000000044E-29.5645100000000136E-20.109277000000000110.106774999999999999.523319999999999E-20.100635000000000118.9636200000000235E-28.5946700000000001E-26.8798800000000077E-27.1383700000000078E-28.5382100000000002E-20.120435000000000110.116776000000000177.5106800000000071E-29.1018700000000008E-29.1537500000000119E-20.108054000000000090.1168880000