Post on 28-Jan-2021
transcript
S1
Supporting Information
Planar Chiral Ferrocenylphosphine-borane Complexes Featuring Agostic-type B‒H···E (E = Hg, Sn) Interactions
Alain C. Tagne Kuate,a,b Roger A. Lalancette,a* F. Jäklea*
aDepartment of Chemistry, Rutgers University-Newark, 73 Warren Street, Newark, NJ 07102,
USA
bDepartment of Chemistry, Faculty of Sciences, University of Dschang, P.O. Box 67, Dschang,
Cameroon
* To whom correspondence should be addressed.
Email: fjaekle@andromeda.rutgers.edu ; rogerlal@andromeda.rutgers.edu
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017
S2
Reaction of rac-5 with PhBCl2: Isolation of FcPPh2·BH3 During the course of our studies we also attempted the synthesis of boron-bridged diferrocenes.
However, we could only isolate the parent species FcPPh2·BH3, presumable due to protonolysis.
The lack of analytical data on FcPPh2·BH3 in the literature encouraged us to perform a full
characterization. The MALDI-TOF mass spectrum of FcPPh2·BH3 showed a molecular ion peak
at m/z = 767.5008, suggesting the presence of a dimer with loss of H2.
Synthetic Procedure: A solution of rac-5 (0.052 g, 0.084 mmol) in toluene (10 mL) was slowly
added to a solution of PhBCl2 (0.007 g, 0.042 mmol, 0.5 equiv) in toluene (2 mL) at ‒27 oC
inside a glovebox. The mixture was stirred at room temperature for two days and heated at 90 oC
overnight in a sealed flask. A grey solid was formed, which was removed by filtration and the
solvent was evaporated in vacuum to leave a yellow-orange residue. The latter was taken in a
minimum of THF and passed through a plug of Al2O3 eluted with THF/hexane. The first band
was concentrated, dissolved in CH2Cl2, layered with hexanes and stored at ‒25 oC. An orange
solid crystallized that was identified to be ferrocenylphosphine-borane adduct FcPPh2·BH3.
Yield: 0.023 g (69%). 1H NMR (499.9 MHz, CDCl3, 25 oC): δ = 7.59 (m, 4H, Ph), 7.47 (m, 2H,
Ph), 7.41 (m, 4H, Ph), 4.51 (nr, 2H, Cp), 4.42 (nr, 2H, Cp), 4.10 (s, 5H, free Cp), 1.25 (brm, 3H,
BH3). 13C{1H} NMR (125.7 MHz, CDCl3, 25 oC): δ = 133.0 (d, 2JP,C = 9 Hz, o-Ph), 131.7 (d, 1JP,C = 59 Hz, i-Ph), 131.2 (s, p-Ph), 128.8 (d, 3JP,C = 10 Hz, m-Ph), 73.1 (d, JP,C = 10 Hz, Cp),
72.2 (d, 1JP,C = 8 Hz, Cp), 70.1 (s, free Cp), 69.1 (d, 1JP,C = 69 Hz, i-Cp-P). 31P{1H} NMR
(202.5 MHz, CDCl3, 25 oC): δ = 16.0 (nr). 11B{1H} NMR (160.4 MHz, CDCl3, 25 oC): ‒38.4
(nr). High-resolution MALDI-TOF MS (positive mode, anthracene): m/z 370.0545
([(FcPPh2)+H]+, 100%, calcd for 12C221H1911B56Fe31P 370.0568).
S3
Figure S1. 1H NMR spectrum of (pS)-3.
Figure S2. Expansions of the 1H NMR spectrum of (pS)-3.
S4
Figure S3a. 13C NMR spectrum of (pS)-3.
Figure S3b. Expansions of the 13C NMR spectrum of (pS)-3.
S5
Figure S4. 11B NMR spectrum of (pS)-3.
Figure S5. 31P NMR spectrum of (pS)-3.
Figure S6. 119Sn NMR spectrum of (pS)-3.
S6
Figure S7a. 1H NMR spectrum of (pS)-4.
S7
Figure S7b. Expansions of the 1H NMR spectrum of (pS)-4.
Figure S8a. 13C NMR spectrum of (pS)-4.
S8
Figure S8b. Expansions of the 13C NMR spectrum of (pS)-4.
S9
Figure S9. 11B NMR spectrum of (pS)-4.
Figure S10. 31P NMR spectrum of (pS)-4.
Figure S11. 119Sn NMR spectrum of (pS)-4.
S10
Figure S12a. 1H NMR spectrum of rac-5.
Figure S12b. Expansions of the 1H NMR spectrum of rac-5.
S11
Figure S13a. 13C NMR spectrum of rac-5.
Figure S13b. Expansions of the 13C NMR spectrum of rac-5.
S12
Figure S14. 11B NMR spectrum of rac-5.
Figure S15. 31P NMR spectrum of rac-5.
S13
Figure S16a. 1H NMR spectrum of (pSpS)-6.
Figure S16b. Expansions of the 1H NMR spectrum of (pSpS)-6.
S14
Figure S17a. 13C NMR spectrum of (pSpS)-6.
Figure S17b. Expansions of the 13C NMR spectrum of (pSpS)-6.
S15
Figure S18. 11B NMR spectrum of (pSpS)-6.
Figure S19. 31P NMR spectrum of (pSpS)-6.
Figure S20a. 1H NMR spectrum of (pSpS)-7.
S16
Figure S20b. Expansions of the 1H NMR spectrum of (pSpS)-7.
S17
Figure S21a. 1H NMR spectrum of (pS)-8.
Figure S21b. Expansions of the 1H NMR spectrum of (pS)-8.
S18
Figure S22a. 13C NMR spectrum of (pS)-8.
Figure S22b. Expansions of the 13C NMR spectrum of (pS)-8.
S19
Figure S23. 11B NMR spectrum of (pS)-8.
Figure S24. 31P NMR spectrum of (pS)-8.
Figure S25. 119Sn NMR spectrum of (pS)-8.
S20
Figure S26a. 1H NMR spectrum of (pRpR)-10.
Figure S26b. Expansions of the 1H NMR spectrum of (pRpR)-10.
S21
Figure S27a. 13C NMR spectrum of (pRpR)-10.
Figure S27b. Expansions of the 13C NMR spectrum of (pRpR)-10.
S22
Figure S28. 11B NMR spectrum of (pRpR)-10.
Figure S29. 31P NMR spectrum of (pRpR)-10.
Figure S30. 119Sn NMR spectrum of (pRpR)-10.
at119_119Sn_101816
60 40 20 0 -20 -40 -60 -80Chemical Shift (ppm)
-13.
088
S23
Figure S31a. 1H NMR spectrum of FcPPh2·BH3.
Figure S31b. Expansions of the 1H NMR spectrum of FcPPh2·BH3.
S24
Figure S32a. 13C NMR spectrum of FcPPh2·BH3.
Figure S32b. Expansions of the 13C NMR spectrum of FcPPh2·BH3.
S25
Figure S33. 11B NMR spectrum of FcPPh2·BH3.
Figure S34. 31P NMR spectrum of FcPPh2·BH3.
S26
Figure S35. MALDI-TOF mass spectrum of (pS)-3.
534.
0228
532.
0165
533.
0197
530.
0114
535.
0241
531.
0130
538.
0336
536.
0285
537.
0322
539.
0282
525.
3925
528.
0095
526.
0083
529.
0152
527.
0086
540.
2598
121416_AT34_calib_1_2 0:A1 MS Raw
0
1
2
3
4
4x10
Inte
ns. [
a.u.
]
534.
0222
532.
0220
533.
0237
530.
0217
531.
0235
535.
0250
536.
0243
538.
0249
539.
0279
528.
0245
537.
0268
529.
0261
526.
0244
527.
0275
540.
0305
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
524 526 528 530 532 534 536 538 540 542
[M–BH3]+
S27
Figure S36. MALDI-TOF mass spectrum of (pS)-4.
568.
0015
565.
9962
569.
0093
564.
9971
566.
9906
564.
0098
570.
0010
121416_AT44_calib_1_1 0:A3 MS Raw
0
50
100
150
200
Inte
ns. [
a.u.
]
568.
0001
566.
0003
567.
0020
565.
0023
564.
0008
569.
0019
569.
9995
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
564 565 566 567 568 569 570
553.
9666
551.
9519
549.
9408
555.
9871
554.
9809
552.
9764
550.
9521
557.
9964
556.
9941
547.
9397
559.
0110
560.
0040
548.
9441
560.
9992
547.
1063
121416_AT44_calib_1_2 0:A3 MS Raw
0.0
0.2
0.4
0.6
0.8
1.0
5x10
Inte
ns. [
a.u.
]
553.
9669
551.
9668
552.
9685
555.
9664
549.
9671
554.
9689
550.
9688
557.
9693
556.
9690
558.
9723
559.
9683
547.
9694
548.
9714
560.
9707
546.
9729
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
548 550 552 554 556 558 560
[M–BH3]+
[M]+
S28
Figure S37. MALDI-TOF mass spectrum of rac-5; the additional peaks at higher molecular weight correspond to [rac-6–BH3]+ (940.0842 Da) and an undetermined dimeric species.
605.
9874
603.
9795
602.
9759 60
4.98
80
606.
9909
607.
9944
601.
9743
609.
0013
609.
9928
600.
9813
599.
9767
121416_AT79_calib_1_1 0:A10 MS Raw
0.0
0.5
1.0
1.5
2.0
2.54x10
Inte
ns. [
a.u.
]
605.
9880
603.
9867
604.
9876
602.
9868
607.
9884
606.
9893
601.
9856
608.
9912
609.
9896
600.
9909
599.
9882
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
600 602 604 606 608 610
[M–BH3]+
S29
Figure S38. MALDI-TOF mass spectrum of (pSpS)-6.
954.
1053
952.
0917
953.
0947
951.
0822
955.
1023
956.
0928
950.
0733
957.
0979
949.
0719
958.
0825
948.
0920
959.
0957
947.
0987
121416_AT100R_calib_1_2 0:A14 MS Raw
0
1
2
3
44x10
Inte
ns. [
a.u.
]
954.
1037
952.
1024
953.
1040
951.
1022
955.
1062
950.
1017
956.
1068
949.
1044
957.
1088
948.
1047
958.
1113
947.
1070
959.
1136
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
948 950 952 954 956 958
940.
0734
938.
0680
941.
0755
937.
0652 9
39.0
696
936.
0558
942.
0749
935.
0703
943.
0773
934.
0598
121516_AT100_cal_1_1 0:A14 MS Raw
0.0
0.2
0.4
0.6
0.8
1.0
4x10
Inte
ns. [
a.u.
]
940.
0703
938.
0688
939.
0703
937.
0682
941.
0729
936.
0676
942.
0735
943.
0757
935.
0720
934.
0701
944.
0782
933.
0762
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
934 936 938 940 942 944
[M–BH3]+
[M–2BH3]+
S30
Figure S39. MALDI-TOF mass spectrum of (pSpS)-7.
905.
0495
903.
0455
904.
0451
901.
0408
906.
0608
902.
0405
907.
0630
909.
0636
908.
0675
910.
0715
899.
0395
900.
0473
897.
0530
911.
0714
898.
0399
121416_AT64_III_calib_1_4 0:A6 MS Raw
0.00
0.25
0.50
0.75
1.00
1.25
4x10
Inte
ns. [
a.u.
]
905.
0517
903.
0517
904.
0533
906.
0542
901.
0513
902.
0531
907.
0547
909.
0543
908.
0566
910.
0569
899.
0543
900.
0561
897.
0538
911.
0596
898.
0569
912.
0621
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
896 898 900 902 904 906 908 910 912
889.
0534
887.
0515
888.
0574
886.
0562
885.
0482
890.
0511
891.
0548
893.
0575
884.
0653
892.
0608
894.
0755
883.
0471
895.
0634
881.
0489
882.
0681
121416_AT64_III_calib_1_4 0:A6 MS Raw
0
1000
2000
3000
4000
5000
Inte
ns. [
a.u.
]
889.
0568
887.
0568
888.
0584
890.
0593
885.
0564
886.
0582
891.
0598
893.
0594
892.
0617
894.
0620
883.
0594
884.
0612
881.
0588
895.
0647
882.
0620
896.
0672
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
882 884 886 888 890 892 894 896
[M–BH3 + O]+
[M–BH3 + H]+
S31
Figure S40. MALDI-TOF mass spectrum of (pS)-8.
533.
0127
534.
9943
531.
0222
532.
0288
534.
0103
530.
0369
529.
0350
536.
0022
537.
0112
538.
9982
528.
0415
538.
0351
527.
0244
540.
0074
121616_AT64_II_cal_1_7 0:I1 MS Raw
0.0
0.5
1.0
1.5
4x10
Inte
ns. [
a.u.
]
534.
9936
532.
9934
533.
9952
530.
9932
531.
9949
535.
9965
536.
9957
538.
9963
539.
9993
528.
9959
537.
9982
529.
9975
526.
9958
527.
9989
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
528 530 532 534 536 538 540
520.
0041
517.
9956
518.
9965
515.
9864
516.
9874
521.
0101
522.
0134
524.
0159
514.
9657
523.
0095
525.
0134
513.
9873
511.
9904
512.
9731
526.
0508
121616_AT64_II_cal_1_7 0:I1 MS Raw
0
1
2
3
4x10
Inte
ns. [
a.u.
]
520.
0065
518.
0063
519.
0081
516.
0061
517.
0078
521.
0094
522.
0086
524.
0092
525.
0122
514.
0089
523.
0111
515.
0104
512.
0087
513.
0119
526.
0148
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
512 514 516 518 520 522 524 526
[M–BH3–H + O]+
[M–BH3]+
S32
Figure S41. MALDI-TOF mass spectrum of (pRpR)-10.
903.
0502
905.
0513
904.
0532
906.
0494
901.
0560
902.
0456
907.
0415
900.
0674
909.
0508
908.
0615
899.
0725
910.
0621
121516_AT119_cal_1_2 0:A16 MS Raw
0
100
200
300
400
500
600
Inte
ns. [
a.u.
]
905.
0517
903.
0517
904.
0533
906.
0542
901.
0513
902.
0531
907.
0547
909.
0543
908.
0566
910.
0569
899.
0543
900.
0561
897.
0538
911.
0596
898.
0569
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
898 900 902 904 906 908 910
889.
0544
887.
0382
888.
0715
890.
0703
885.
0188
891.
0876
886.
0578
893.
0750
892.
0986
894.
0884
883.
0214
884.
0613
892.
6449
881.
0188
882.
0209
895.
1011
879.
0203
880.
0514
121416_AT119_calib_1_2 0:B16 MS Raw
0.00
0.25
0.50
0.75
1.00
1.25
5x10
Inte
ns. [
a.u.
]
889.
0568
887.
0568
888.
0584
890.
0593
885.
0564
886.
0582
891.
0598
893.
0594
892.
0617
894.
0620
883.
0594
884.
0612
881.
0588
895.
0647
882.
0620
896.
0672
879.
0629
880.
0661
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
880 882 884 886 888 890 892 894 896
[M–2BH3 + O]+
[M–2BH3 + H]+
S33
Figure S42. MALDI-TOF mass spectrum of FcPPh2·BH3.
370.
0545
371.
0744
368.
0526
372.
0682
369.
0488
373.
0627
121916_FcPPh2BH3_II_cal_1_3 0:E11 MS Raw
0
1
2
3
4
5
4x10
Inte
ns. [
a.u.
]
370.
0568
371.
0600
368.
0615
372.
0624
369.
0649
373.
0646
0
500
1000
1500
2000
Inte
ns. [
a.u.
]
364 366 368 370 372 374 376 378
[M–2BH3 + O]+
[M–BH3 + H]+
S3
4
Tab
le S
1. C
ryst
al d
ata
and
stru
ctur
e re
finem
ent d
etai
ls fo
r (pS
)-3,
(pS)
-4, r
ac-5
, and
(pSp
S)-7
.
Com
poun
d (p
S)-3
(p
S)-4
ra
c-5
(pSp
S)-7
em
piric
al fo
rmul
a C
25H
30B
FePS
n C
24H
27B
ClF
ePSn
C
22H
21B
ClF
eHg
P C
46H
45B
Fe2P
2Sn
MW
54
6.81
56
7.22
61
9.06
90
0.96
T,
K
100
100
100
100
wav
elen
gth,
Å
1.54
178
1.54
178
1.54
178
1.54
178
crys
tal s
yste
m
Orth
orho
mbi
c O
rthor
hom
bic
Orth
orho
mbi
c O
rthor
hom
bic
spac
e gr
oup
P212
121
P212
121
Pbca
P2
1212
1 a,
Å
7.45
43(2
) 7.
3385
(2)
15.7
369(
8)
10.8
780(
2)
b, Å
16
.414
1(4)
16
.586
7(4)
15
.009
5(7)
17
.554
3(4)
c,
Å
19.3
128(
4)
19.1
137(
5)
17.5
758(
8)
20.7
334(
5)
α, d
eg
90
90
90
90
β, d
eg
90
90
90
90
γ, de
g 90
90
90
90
V,
Å3
2363
.0(1
) 23
26.5
(1)
4151
.5(3
) 39
59.1
6(15
) Z
4 4
8 4
ρ cal
c, g
cm-3
1.
537
1.61
9 1.
981
1.51
2 µ
(Cu
Kα
), m
m-1
14
.01
15.2
9 20
.61
11.7
8 cr
ysta
l siz
e, m
m
0.38×0
.21×
0.18
0.
26×0
.21×
0.07
0.
26×0
.18×
0.11
0.
29×0
.23×
0.17
θ
rang
e, d
eg
3.5–
70.5
3.
5–69
.5
4.8–
68.7
3.
3–68
.8
limiti
ng in
dice
s –8
≤ h
≤ 8
–2
0 ≤
k ≤
19
–23 ≤
l ≤ 2
2
–6 ≤
h ≤
8
–20 ≤
k ≤
18
–21 ≤
l ≤ 2
3
–16 ≤
h ≤
17
–17 ≤
k ≤
18
–20 ≤
l ≤ 2
0
–12 ≤
h ≤
12
–20 ≤
k ≤
21
–24 ≤
l ≤ 2
4 re
flns c
olle
cted
21
972
1595
5 36
723
3474
5 in
depe
nden
t ref
lns
4183
[R
(int)
= 0.
036]
38
13
[R(in
t) =
0.02
6]
3696
[R
(int)
= 0.
040]
68
72
[R(in
t) =
0.05
0]
abso
rptio
n co
rrec
tion
Num
eric
al
Num
eric
al
Num
eric
al
Num
eric
al
data
/rest
rain
ts/p
aram
eter
s 41
83/3
/274
38
13/0
/273
36
96/0
/256
68
72/3
/480
go
odne
ss-o
f-fit
on
F2
1.05
1.
03
1.13
0.
98
final
R in
dice
s, [ I
>2σ
(I) ]
[a]
0.01
6, w
R2 =
0.0
40
0.01
8, w
R2 =
0.0
38
0.02
2, w
R2 =
0.0
67
0.02
1, w
R2 =
0.0
44
R in
dice
s (al
l dat
a) [a
] 0.
017
0.01
9 0.
0256
0.
022
peak
max
/hol
e min
(e Å
–3)
0.38
/ –0
.35
0.50
/ –0
.41
0.83
/ –1
.15
0.27
/ –0
.31
abso
lute
stru
ctur
e pa
ram
eter
0.
038(
3)
0.02
0(3)
-
0.02
7(2)
[a] R1 = Σ||F o|–|F
c||/Σ|F
o|; w
R2 = {Σ[w
(Fo2
–Fc2) 2]/Σ[w(F
o2) 2]}1/2
S35
Computational Details for the Optimized Structures of (pS)-3 and (pS)-4
Compound (pS)-3
Stoichiometry C25H30BFePSn Framework group C1[X(C25H30BFePSn)] Deg. of freedom 171 Full point group C1 NOp 1 Largest Abelian subgroup C1 NOp 1 Largest concise Abelian subgroup C1 NOp 1 Selected Distances: H1···Sn1 = 3.129 Å, P1–B1 = 1.939 Å Standard orientation: Center Number Atomic Number Coordinates (Angstroms)
X Y Z
1 50 -2.58529 1.199284 0.337887 2 26 -0.790654 -1.935737 -0.611357 3 15 1.399948 0.439541 0.551407 4 5 0.739987 0.709201 2.337561 5 1 -0.091022 1.54001 2.151053 6 1 1.660059 1.215123 2.897112 7 1 0.398522 -0.358819 2.747869 8 6 -1.170403 0.07523 -0.810315 9 6 0.263758 -0.185455 -0.683922 10 6 0.655404 -1.062638 -1.769566 11 1 1.57566 -1.42283 -1.932356 12 6 -0.498517 -1.331822 -2.559508 13 1 -0.535087 -1.916885 -3.369736 14 6 -1.592088 -0.638033 -1.97695 15 1 -2.531896 -0.673382 -2.312814 16 6 -1.957743 -2.622607 0.930012 17 1 -2.604682 -2.076636 1.462663 18 6 -0.589706 -2.819927 1.234482 19 1 -0.103202 -2.435735 2.018957 20 6 -0.024525 -3.648508 0.22594 21 1 0.926355 -3.956572 0.177106 22 6 -1.050772 -3.954385 -0.702215 23 1 -0.952316 -4.521314 -1.520511 24 6 -2.250903 -3.322901 -0.267319 25 1 -3.140851 -3.367902 -0.721499 26 6 2.837419 -0.679918 0.453404 27 6 3.763507 -0.580296 -0.588939 28 1 3.664508 0.095568 -1.249582 29 6 4.826001 -1.463959 -0.657907 30 1 5.443169 -1.407464 -1.377637 31 6 4.993319 -2.437421 0.32516
S36
32 1 5.731654 -3.034477 0.284395 33 6 4.086155 -2.527813 1.356291 34 1 4.202716 -3.189376 2.027935 35 6 2.997506 -1.661788 1.423586 36 1 2.36777 -1.740552 2.131064 37 6 2.024339 2.03581 -0.066649 38 6 1.291715 2.826815 -0.936768 39 1 0.47601 2.496789 -1.296752 40 6 1.732783 4.09086 -1.290692 41 1 1.216565 4.627576 -1.880302 42 6 2.930994 4.576753 -0.779261 43 1 3.238723 5.442151 -1.022571 44 6 3.674737 3.791711 0.08608 45 1 4.498531 4.119828 0.428179 46 6 3.231018 2.530027 0.458346 47 1 3.739736 2.004961 1.06451 48 6 -4.412613 0.876052 -0.758687 49 1 -5.167185 1.243732 -0.252387 50 1 -4.545997 -0.085714 -0.892856 51 1 -4.35292 1.322257 -1.629088 52 6 -2.91545 0.560593 2.368493 53 1 -2.167507 -0.002804 2.658403 54 1 -3.750285 0.046688 2.417337 55 1 -2.978767 1.344524 2.951408 56 6 -2.046557 3.267888 0.334065 57 1 -1.163399 3.375373 0.743673 58 1 -2.707308 3.778643 0.844827 59 1 -2.02146 3.597443 -0.589347
S37
Compound (pS)-4
Stoichiometry C24H27BClFePSn Framework group C1[X(C24H27BClFePSn)] Deg. of freedom 162 Full point group C1 NOp 1 Largest Abelian subgroup C1 NOp 1 Largest concise Abelian subgroup C1 NOp 1 Selected Distances: H1···Sn1 = 2.631 Å, P1–B1 = 1.944 Å Standard orientation:
Center Number Atomic Number Coordinates (Angstroms)
X Y Z
1 50 -2.387491 1.053314 0.483656 2 26 -0.581954 -1.988349 -0.608665 3 17 -4.413978 0.647573 -0.741682 4 15 1.506943 0.497409 0.486467 5 5 0.731641 0.783261 2.225411 6 1 -0.135303 1.493664 1.988938 7 1 1.559874 1.289407 2.768124 8 1 0.454398 -0.182868 2.686438 9 6 -1.051563 -0.007618 -0.796202 10 6 0.380792 -0.192745 -0.724452 11 6 0.768098 -1.053679 -1.82369 12 1 1.695888 -1.370848 -2.021881 13 6 -0.392187 -1.37801 -2.560602 14 1 -0.429195 -1.969557 -3.365233 15 6 -1.503912 -0.740575 -1.944024 16 1 -2.454978 -0.815386 -2.246204 17 6 -1.745885 -2.757035 0.892977 18 1 -2.458775 -2.260495 1.38665 19 6 -0.389626 -2.826751 1.265923 20 1 0.025492 -2.395025 2.064962 21 6 0.28166 -3.607091 0.297166 22 1 1.257278 -3.826917 0.296554 23 6 -0.666676 -4.02463 -0.677975 24 1 -0.479761 -4.597013 -1.476591 25 6 -1.93308 -3.48983 -0.299277 26 1 -2.797622 -3.615034 -0.78561 27 6 2.066287 2.1125 -0.133623 28 6 1.232687 2.92263 -0.892193
S38
29 1 0.400481 2.584349 -1.2042 30 6 1.606482 4.225473 -1.202454 31 1 1.030393 4.77083 -1.725891 32 6 2.807298 4.730431 -0.750716 33 1 3.054246 5.625762 -0.951504 34 6 3.658284 3.921068 0.000565 35 1 4.496516 4.256278 0.293698 36 6 3.278619 2.629793 0.31862 37 1 3.850403 2.091511 0.852564 38 6 2.971578 -0.569082 0.426114 39 6 3.191457 -1.48142 1.436744 40 1 2.579852 -1.541903 2.161109 41 6 4.305864 -2.314384 1.399448 42 1 4.456598 -2.932401 2.1063 43 6 5.191114 -2.253965 0.346876 44 1 5.94783 -2.826981 0.322829 45 6 4.968048 -1.346089 -0.678138 46 1 5.564936 -1.310459 -1.41635 47 6 3.880512 -0.494362 -0.632667 48 1 3.748843 0.143066 -1.323557 49 6 -2.868549 0.319819 2.440408 50 1 -2.84552 1.060101 3.081112 51 1 -2.213835 -0.36047 2.703667 52 1 -3.76467 -0.077096 2.428536 53 6 -2.175888 3.165855 0.33518 54 1 -1.269819 3.423756 0.605279 55 1 -2.828189 3.601773 0.924183 56 1 -2.333224 3.445351 -0.590963
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Second Order Perturbation Theory Analysis of Fock Matrix in NBO Basis Compound (pS)-3:
E(2) E(j)-E(i) F(i,j) Donor NBO (i) Acceptor NBO (j) kcal/mol a.u. a.u. 8. BD (1) B4 - H5 / 133. LP*(1)Sn1 0.20 0.40 0.009
Compound (pS)-4: E(2) E(j)-E(i) F(i,j)
Donor NBO (i) Acceptor NBO (j) kcal/mol a.u. a.u. 7. BD (1) B5 - H6 / 134. LP*(2)Sn1 5.46 0.37 0.043
Atoms in Molecules (AIM) Analysis of Compound (pS)-4: Electron Density and Laplacian of the Electron Density at the BCPs: BCP # Name Atoms Rho DelSqRho Ellipticity K BPL - GBL_I 1 1 BCP1 Sn1-C9 0.058257 +0.441543 0.098363 +0.003085 0.000321 2 2 BCP2 Sn1-Cl3 0.031057 +0.263762 0.180649 +0.000203 0.001279 3 3 BCP3 Sn1-H6 0.008196 +0.040694 3.173225 -0.001239 0.027879 4 4 BCP4 P4-B5 0.117967 -0.123341 0.015182 +0.091664 0.000114 5 5 BCP5 B5-H6 0.163606 -0.186163 0.031616 +0.152568 0.000261 6 6 BCP6 B5-H7 0.167393 -0.261977 0.015456 +0.157056 0.000111 7 7 BCP7 B5-H8 0.165492 -0.233826 0.024250 +0.155217 0.000133 8 8 BCP8 Cl3-H16 0.006648 +0.026096 0.304853 -0.001318 0.109756 9 9 BCP9 Fe2-C10 0.053785 +0.263912 1.829033 +0.015711 0.379691 10 10 BCP10 P4-C10 0.167724 -0.281002 0.033883 +0.165734 0.001202 11 11 BCP11 C9-C10 0.282342 -0.794933 0.036028 +0.273013 0.020816 12 12 BCP12 C10-C11 0.291520 -0.729070 0.485689 +0.290491 0.009605 13 13 BCP13 C11-H12 0.279412 -0.986564 0.019557 +0.279439 0.001116 14 14 BCP14 C11-C13 0.295221 -0.823018 0.149306 +0.305908 0.089367 15 15 BCP15 Fe2-C13 0.049639 +0.369907 0.128523 +0.010907 0.170992 16 16 BCP16 C13-C15 0.294591 -0.824166 0.162673 +0.304573 0.087089 17 17 BCP17 C13-H14 0.277657 -0.885774 0.142848 +0.275465 0.010568 18 18 BCP18 Fe2-C9 0.053177 +0.250908 1.486597 +0.017293 0.272246 19 19 BCP19 C9-C15 0.296944 -0.735719 0.420427 +0.301185 0.023736 20 20 BCP20 C15-H16 0.280408 -0.981077 0.025007 +0.278860 0.000970 21 21 BCP21 Fe2-C19 0.049804 +0.265852 1.730782 +0.013919 0.951930 22 22 BCP22 Fe2-C21 0.049772 +0.274336 1.635907 +0.013260 1.013026 23 23 BCP23 C17-H18 0.279963 -0.983094 0.024664 +0.280751 0.001585 24 24 BCP24 H20-H40 0.003597 +0.012389 0.850014 -0.000924 0.383545 25 25 BCP25 H8-H20 0.005453 +0.018013 0.104974 -0.001096 0.077273 26 26 BCP26 Fe2-C25 0.051402 +0.381232 0.074650 +0.011728 0.146277 27 27 BCP27 C17-C19 0.301656 -0.801494 0.508203 +0.308525 0.011939 28 28 BCP28 C19-H20 0.280003 -0.985321 0.024571 +0.280537 0.001692 29 29 BCP29 C21-C23 0.300241 -0.794696 0.507503 +0.305909 0.012389 30 30 BCP30 C19-C21 0.293798 -0.952076 0.057943 +0.298352 0.002183 31 31 BCP31 C21-H22 0.278303 -0.975457 0.025058 +0.277941 0.001693 32 32 BCP32 C23-C25 0.293044 -0.799945 0.165894 +0.300031 0.089186 33 33 BCP33 C17-C25 0.293775 -0.806941 0.164471 +0.301336 0.088000 34 34 BCP34 C23-H24 0.277909 -0.972062 0.023815 +0.277608 0.001547 35 35 BCP35 C25-H26 0.277897 -0.888962 0.141866 +0.275800 0.009718 36 36 BCP36 P4-C27 0.163534 -0.301138 0.040719 +0.159916 0.000486 37 37 BCP37 C27-H54 0.002591 +0.006043 0.356704 -0.000427 0.248583 38 38 BCP38 C27-C28 0.299227 -0.812036 0.488411 +0.315439 0.000105 39 39 BCP39 C28-H29 0.280761 -0.988600 0.022208 +0.281177 0.000073 40 40 BCP40 C28-C30 0.304601 -1.061286 0.036974 +0.324759 0.000139 41 41 BCP41 C30-C32 0.304935 -0.871338 0.514585 +0.326585 0.000119
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Experimental IR Spectral Data and Calculated Frequencies
ATR-FTIR analysis of compound (pS)-3 revealed two strong and broad absorption bands at 2403 and 2378 cm-1 corresponding to the B‒H stretching frequencies. These bands are significantly shifted to 2417 and 2314 cm-1 in the IR spectrum of (pS)-4. DFT frequency calculations of the optimized structures predict absorption bands for 3 at 2462, 2524, and 2538 cm-1; and for (pS)-4 at 2443, 2505 and 2546 cm-1. According to the computed results, the B‒H stretching frequencies involved in an agostic-type interaction with the tin atom are assigned to be those at 2538 ((pS)-3) and 2443 ((pS)-4) cm-1, which suggests a bathochromic shift of 95 cm-1 that is similar to the bathochromic shift (89 cm-1) when comparing the experimentally observed bands at 2403 cm-1 in (pS)-3 and 2314 cm-1 in (pS)-4. The ATR-FTIR spectra of the parent compound FcPPh2·BH3 showed a broad absorption band at 2380 cm-1.
S41
Calculated Frequencies for Compound (pS)-3: Frequencies -- 2461.5186 2523.5996 2538.2687 Red. masses -- 1.0279 1.1106 1.1117 Frc consts -- 3.6695 4.1673 4.2202 IR Inten -- 44.7466 160.6705 139.2541
Atom AN X Y Z X Y Z X Y Z 4 5 0 -0.01 -0.04 -0.09 -0.05 -0.02 -0.05 0.09 -0.02 5 1 -0.36 0.31 -0.03 0.25 -0.23 0.01 0.62 -0.52 0.03 6 1 0.54 0.25 0.35 0.54 0.25 0.38 0.08 0.05 0.05 7 1 -0.15 -0.5 0.15 0.16 0.56 -0.19 -0.17 -0.52 0.17
Calculated Frequencies for Compound (pS)-4: Frequencies -- 2442.6894 2505.4818 2545.7510 Red. masses -- 1.0442 1.0872 1.1146 Frc consts -- 3.6709 4.0209 4.2561 IR Inten -- 197.7806 163.3441 118.9582
Atom AN X Y Z X Y Z X Y Z 5 5 -0.05 0.03 0.01 0.06 -0.04 0.06 -0.05 -0.09 -0.01 6 1 0.73 -0.5 0.14 -0.34 0.23 -0.05 -0.03 0 0 7 1 -0.22 -0.15 -0.17 -0.44 -0.35 -0.38 0.44 0.32 0.38 8 1 0.06 0.29 -0.1 0.15 0.55 -0.2 0.16 0.68 -0.26
S42
References:
1. M. A. Bennet, M. Contel, D. C. R. Hockless, L. L. Welling, A. C. Willis, Inorg. Chem.
2002, 41, 844-855.
2. The following van der Waals radii are used: H 1.10, B 1.92, O 1.52, P 1.80, Cl 1.75, Sn
2.17, Hg 2.05 Å; see M. Mantina, A. C. Chamberlin, R. Valero, C. J. Cramer, D. G.
Truhlar J. Phys. Chem. A, 2009, 113, 5806-5812; the value of 2.05 Å for Hg is taken
from S. S. Batsanov, J. Mol. Struct. 1999, 468, 151-159.