Supporting Information Synthesis, Structures, and Catalytic Reactivity of Bis(N- Heterocyclic Carbene) Supported Diphenyldiazomethane and 1- Azidoadamantane Complexes of Nickel Nicole D. Harrold,* Amanda R. Corcos,‡ and Gregory L. HillhouseGordon Center for Integrative Science, Department of Chemistry, The University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, USA ‡ Present Address: Department of Chemistry, University of Wisconsin at Madison, Madison, WI 53706, USA. Deceased March 6, 2014. * To whom correspondence should be addressed: [email protected]S1. Experimental Section S 2 Synthesis of (IMes) 2 Ni (1-IMes) S2 Synthesis of (SIMes) 2 Ni (1-SIMes) S2 Synthesis of (IPr) 2 NiCl 2 (2) S2 Synthesis of (IPr) 2 Ni (1-IPr). S2 S2. Crystallography Tables S 4 Table S1. Crystal Data for 3-IMes2C 7 H 8 , 3-SIMes, 3-IPrC 4 H 10 O, and 4. S4 Table S2. Selected bond distances for 3-IMes S5 Table S3. Selected bond distances for 3-SIMes S6 Table S4. Selected bond distances for 3-IPr S7 Table S5. Selected bond distances for 4 S8 Table S6. Selected bond angles for 3-IMes S9 Table S7. Selected bond angles for 3-SIMes S10 Table S8. Selected bond angles for 3-IPr S11 S-1
Transcript
Supporting Information
Synthesis, Structures, and Catalytic Reactivity of Bis(N-Heterocyclic Carbene) Supported
Diphenyldiazomethane and 1-Azidoadamantane Complexes of Nickel
Nicole D. Harrold,* Amanda R. Corcos,‡ and Gregory L. Hillhouse Gordon Center for Integrative Science, Department of Chemistry, The University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, USA
‡ Present Address: Department of Chemistry, University of Wisconsin at Madison, Madison, WI 53706, USA.
S1. Experimental Section S 2Synthesis of (IMes)2Ni (1-IMes) S2Synthesis of (SIMes)2Ni (1-SIMes) S2Synthesis of (IPr)2NiCl2 (2) S2Synthesis of (IPr)2Ni (1-IPr). S2
S2. Crystallography Tables S 4Table S1. Crystal Data for 3-IMes2C7H8, 3-SIMes, 3-IPrC4H10O, and 4. S4Table S2. Selected bond distances for 3-IMes S5Table S3. Selected bond distances for 3-SIMes S6Table S4. Selected bond distances for 3-IPr S7Table S5. Selected bond distances for 4 S8Table S6. Selected bond angles for 3-IMes S9Table S7. Selected bond angles for 3-SIMes S10Table S8. Selected bond angles for 3-IPr S11Table S9. Selected bond angles for 4 S12
S3. 1H, 13C, and Mass Spectra S 13S4. References S 29
S-1
S1. Experimental Section.
Synthesis of (IMes)2Ni (1-IMes). Bis(1,5-cyclooctadiene)nickel(0) (0.50 g, 1.82 mmol) was
dissolved in diethyl ether (20 mL). A solution of IMes (1.10 g, 3.64 mmol) in diethyl ether (20
mL) was slowly added at room temperature. A very dark purple colored solution was obtained.
After the mixture was stirred for 20 minutes the volatiles were removed under reduced pressure.
The solid was dissolved in 10 mL of n-pentane and cooled at -35 C to give 1.09 g, 90 %, of 1-
IMes as dark purple crystals. Spectroscopic characterization matched the previously reported
data.1
Synthesis of (SIMes)2Ni (1-SIMes). Bis(1,5-cyclooctadiene)nickel(0) (0.50 g, 1.82 mmol) was
dissolved in diethyl ether (20 mL). A solution of SIMes (1.12 g, 3.64 mmol) in diethyl ether (20
mL) was slowly added at room temperature. A very dark purple colored solution was obtained.
After the mixture was stirred for 20 minutes the volatiles were removed under reduced pressure.
The solid was dissolved in 10 mL of n-pentane and cooled at -35 C to give 1.12 g (92 %) of 1-
SIMes as dark purple crystals. 1H NMR (298 K, 500.13 MHz, C6D6): 6.73 (s, 8H, C6H2), 3.80
was dissolved in diethyl ether (20 mL). A solution of IPr (1.41 g, 3.64 mmol) in diethyl ether (20
mL) was slowly added at room temperature. A very dark purple colored solution was obtained.
After the mixture was stirred overnight the volatiles were removed under reduced pressure. The
solid was dissolved in 10 mL of n-pentane and cooled at -35 C to give a mixture of 1-IPr and
S-2
starting materials. Spectroscopic characterization matched the previously reported data.2 Method
B: 1.0 g (1.10 mmol) 2 was suspended in 15 mL thf and cooled to -45 C. To the light pink
suspension 313 mg (2.32 mmol, 2.1 equiv.) of freshly prepared KC8 was added via spatula. The
solution immediately turned deep purple in color. The solution was filtered through celite and the
filtrate was reduced to dryness resulting in pure 1-IPr. Yield: 0.737 g, 80 %. Spectroscopic
characterization matched the previously reported data.2
S-3
Table S1. Crystal Data for 3-IMes2C7H8, 3-SIMes, 3-IPrC4H10O, and 4.Identification code 3-IMes2C7H8 3-SIMes 3-IPrC4H10O 4Empirical formula C69 H74 N6 Ni1 C55 H62 N6 Ni1 C71 H92 N6 Ni1 O1 C52 H63 N7 Ni1
Formula weight 1046.05 865.81 1104.21 924.04Temperature 100(1) K 100(2) K 100(2) K 100(2) KWavelength 0.71073 Å 0.71073 Å 0.71073 Å 0.71073 ÅCrystal system Monoclinic Monoclinic Triclinic TriclinicSpace group P 21/c P 21 P-1 P-1Unit cell dimensions a = 12.753(3) Å a = 10.3482(8) Å a = 12.623(2) Å a = 10.023(2) Å
b = 23.623(7) Å b = 18.521(2) Å b = 12.812(2) Å b = 11.221(3) Åc = 20.190(6) Å c = 12.345(1) Å c = 20.291(4) Å c = 22.819(5) Å = 90 = 90 = 87.014(4) = 81.701(4)° = 108.016(5) = 92.163(2) = 74.453(3) = 84.728(4)° = 90 = 90 = 80.135(4) = 78.702(4)°
1. Arduengo III, A. J.; Gamper, S. F.; Calabrese, J. C.; Davidson, F. J. Am. Chem. Soc. 1994, 116 (10), 4391.2. Matsubara, K.; Ueno, K.; Shibata, Y. Organometallics 2006, 25 (14), 3422.
