Article
Organometallics, Vol. 29, No. 13, 2010 2915
CHMe2), 2.49 (sept, J = 6.7 Hz, 2H, CHMe2), 1.85 (s, 6H,
NCMe),1.72 (s, 6H, NCMe), 1.51 (s, 6H, NCMe), 1.18 (d, J =
6.8 Hz, 12H, CHMe), 1.14 (d, J = 6.9 Hz, 12H, CHMe), 1.11 (d,
J = 6.8 Hz, 6H, CHMe), 1.10 (d, J = 6.8 Hz, 12H, CHMe), 1.06
(d, J = 6.8 Hz, 6H, CHMe), δ 0.98 (d, J = 6.8 Hz, 12H, CHMe),
0.89 (d, J = 6.7 Hz, 6H, CHMe), 0.85 (d, J = 6.9 Hz, 6H,
CHMe). 13C{1H} NMR (100 MHz, CDCl3): δ 171.38 (NCMe),
169.97 (NCMe), 164.34 (NCMe), 146.46 (o-C), 141.48 (o-C),
137.03 (ipso-C), 136.46 (ipso-C), 123.50 (ArC), 123.21 (ArC),
122.99 (ArC), 122.89 (ArC), 122.76 (ArC), 122.63 (ArC), 121.92
Key Chemical Shifts for 2. N,N0-bound ligand: 1H NMR (399
MHz, CDCl3, 303 K) δ 4.75 (s, 1H, γ-CH), 3.33 (sept, J = 6.4 Hz,
4H, CHMe2), 1.72 (s, 6H, NCMe), 1.18 (d, J = 6.8 Hz, 12H,
CHMe), 1.14 (d, J = 6.9 Hz, 12H, CHMe);13C{1H} NMR (100
MHz, CDCl3) 164.34 (NCMe), (ipso-C), 141.48 (o-C), 141.26 (o-C),
96.23 (γ-C), 27.78 (CHMe), 27.69 (CHMe), 25.32 (NCMe), 24.48
(CHMe). γ-bound ligand: 1H NMR (399 MHz, CDCl3, 303 K) δ
3.71 (s, 1H, γ-CH), 2.91 (m, 2H, CHMe2), 2.49 (sept, J = 6.7 Hz,
2H, CHMe2), 1.51 (s, 6H, NCMe), 0.98 (d, J = 6.8 Hz, 12H,
CHMe), 0.89 (d, J = 6.7 Hz, 6H, CHMe), 0.85 (d, J = 6.9 Hz, 6H,
CHMe); 13C{1H} NMR (399 MHz, CDCl3) δ 169.97 (NCMe),
137.03 (ipso-C), 66.69 (γ-C), 28.21 (CHMe), 28.51 (CHMe), 23.75
(CHMe), 23.20 (CHMe), 22.49 (CHMe), 21.40 (NCMe).
Computational Details. All calculations were performed using
the density function theory in the Gaussian 03 program. The
geometry optimization was performed at the B3LYP level by
using a double-ζ basis set (LanL2DZ) along with the effective
core potential (LanL2ECP) for the Hg atom and the 3-21G basis
set for all other atoms. Zero-point vibrational energy correc-
tions were also included.36,37 1H NMR spectra were estimated
with the gauge invariant atomic orbital DFT (GIAO-DFT)
calculations at the B3LYP/LanL2DZ/3-21G level.
(
ArC), 96.23 (γ-C), 77.72 (γ-C), 66.69 (γ-C), 28.51 (CHMe),
28.51 (CHMe), 28.21 (CHMe), 27.78 (CHMe), 27.69 (CHMe),
25.32 (NCMe), 24.48 (CHMe), 23.75 (CHMe), 23.20 (CHMe),
22.97 (CHMe), 22.49 (CHMe), 21.91 (NCMe), 21.40 (NCMe).
199Hg NMR (71.5 MHz, CDCl3, 303 K): δ -989.7. IR (Nujol,
cm-1): 3050, 1921, 1866, 1806, 1720, 1648 (s), 1624 (s), 1589 (s),
1439 (s), 1358 (s),1328 (s), 1245, 1207 (s), 1188 (s), 1163 (s), 1107,
1068, 1059, 1042, 972, 936, 916, 789 (s), 760 (s), 690, 523. IR
(CCl4, cm-1): 3061 (w), 2963, 2869, 2990 (br), 2004 (br), 1856
(br), 1635, 1549 (br, s), 1461, 1436, 1409, 1382, 1363, 1322, 1253
(s), 1216 (s), 1165 (w). Anal. Calcd: C, 67.25; H, 7.98; N, 5.41.
Found: C, 67.16; H, 8.07; N, 5.39.
Key Chemical Shifts for 1. 1H NMR (399 MHz, CDCl3, 303
K): δ 3.98 (s, 1H, γ-CH), 2.97 (sept, J = 6.8 Hz, 2H, CHMe2),
2.81 (sept, J = 6.9 Hz, 2H, CHMe2), 1.85 (s, 6H, NCMe), 1.11
(d, J = 6.8 Hz, 6H, CHMe), 1.10 (d, J = 6.8 Hz, 12H, CHMe),
0.8 (d, J = 6.8 Hz, 6H, CHMe). 13C{1H} NMR (100 MHz,
CDCl3): δ 171.38 (NCMe), 146.46 (o-C), 136.46 (ipso-C), 77.72
(γ -C), 28.51 (CHMe), 23.20 (CHMe), 22.97 (CHMe), 21.91
(NCMe).
Acknowledgment. We are grateful for financial sup-
port from the EPSRC (LF, Grant No. EP/E032575/1).
Supporting Information Available: Figures giving a van’t Hoff
plot of the equilibria between 1 and 2, variable-temperature 1H
NMR spectra showing resonances between δ 8 and 0 ppm, and
1H-13C gHSQCAD and 1H-13C gHMBCAD spectra, a table
giving Cartesian coordinates of the optimized structures of
1 and 2, text giving the complete ref 31, and a CIF file giving
crystallographic data for complex 1. This material is available
(36) Frisch, M. J. et al. In Gaussian 03, Revision E.01; Gaussian, Inc.,
Wallingford, CT, 2004.
(37) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.