4956 Organometallics, Vol. 28, No. 17, 2009
Arquier et al.
525 [M-Cl-p-cymene]+. IR (KBr): ν 3055 (m), 3043 (m), 2960
(m), 1603 (w), 1573 (s), 1550 (s), 1433 (s), 1371 (s), 1335 (s), 1093
(m), 791 (s), 698 (s), 527 (s) cm-1. Crystal data: see Supporting
Information.
(d, JC-P = 32.3 Hz, PCH(CH3)2), 21.0 (s, NCH(CH3)2), 20.2
(s, NCH(CH3)2), 17.2 (d, JC-P =25.6 Hz, PCH(CH3)2) ppm.
31P{1H} NMR (121.5 MHz, CD2Cl2): δ 113.5 ppm. DCI MS
(CH4, positive mode): m/z 492 [M]+, 457 [M - Cl]+. IR (KBr):
ν 3048 (w), 2957 (w), 1566 (s), 1559 (s), 1371 (w), 1345 (w), 1039
(w) cm-1. Crystal data: see Supporting Information.
8b. Mp: 264-265 °C (dec). 1H NMR (200.1 MHz, CDCl3): δ
7.54-7.25 (m, 5H, C6H5), 5.55-5.47 (m, 4H, C6H4(p-cymene)),
4.22-4.00 (br m, 1H, NCH(CH3)2), 3.90-3.56 (br m, 1H, NCH-
(CH3)2), 2.91 (sept, JH-H = 7.0 Hz, 1H, CH(CH3)2(p-cymene)),
2.35-2.14 (m, 2H, PCH(CH3)2), 2.14 (s, 3H, CH3(p-cymene)),
1.74-1.53 (br m, 6H, NCH(CH3)2), 1.31 (d, JH-H=7.0 Hz, 6H,
CH(CH3)2(p-cymene)), 1.27-1.10 (m, 6H, NCH(CH3)2), 1.05 (dd,
JH-H=7.0 Hz and JH-P=14.4 Hz, 6H, PCH(CH3)2), 0.92 (dd,
JH-H = 7.1 Hz and JH-P = 13.8 Hz, 6H, PCH(CH3)2) ppm.
13C{1H} NMR (50.3 MHz, CDCl3): δ 161.7 (d, JC-P=5.8 Hz,
C(Ph)dN), 137.5 (d, JC-P =3.72 Hz, C6H5), 129.4 (s, C6H5),
129.0 (s, C6H5), 128.1 (s, C6H5), 109.0 (s, C6H4(p-cymene)), 95.7 (s,
C6H4(p-cymene)), 87.5 (d, JC-P=3.5 Hz, C6H4(p-cymene)), 85.2 (d,
JC-P = 4.3 Hz, C6H4(p-cymene)), 52.6 (s, NCH(CH3)2), 46.6
Synthesis of Complex 11. A solution of [(p-cymene)RuCl2]2
(106 mg, 0.17 mmol) in 7 mL of dichloromethane was slowly
added to a solution of i-Pr2N-C(H)dN-PPh2 (10) (128 mg,
0.41 mmol) in 3 mL of dichloromethane at room temperature.
The reaction mixture was allowed to stir for 3 h, the solvent was
removed, and the orange solid was washed with pentane (3 ꢀ 10
mL) and dried under vacuum to give 87% (183 mg) yield of 11.
Suitable crystals were obtained from a saturated dichloro-
1
methane solution at 4 °C. Mp: 104-106 °C (dec). H NMR
(200.1 MHz, CDCl3): δ 8.05 (d, JH-P=22.5 Hz, 1H, C(H)dN),
7.95-7.85 (m, 4H, C6H5), 7.36-7.29 (m, 6H, C6H5), 5.09 (br s,
4H, C6H4(p-cymene)), 4.81 (sept, JH-H = 6.8 Hz, 1H, NCH-
(CH3)2), 3.48 (sept, JH-H = 6.8 Hz, 1H, NCH(CH3)2), 2.69
(sept, JH-H = 6.9 Hz, 1H, CH(CH3)2(p-cymene)), 1.82 (s, 3H,
CH3(p-cymene)), 1.23 (d, JH-H=6.8 Hz, 6H, NCH(CH3)2), 1.11
(d, JH-H=6.8 Hz, 6H, NCH(CH3)2), 1.02 (d, JH-H=6.9 Hz, 6H,
CH(CH3)2(p-cymene)) ppm. 13C{1H} NMR (50.3 MHz, CDCl3): δ
158.5 (d, JC-P=8.6 Hz, C(H)dN), 139.2 (d, JC-P =52.3 Hz,
C6H5), 132.8 (d, JC-P=10.1 Hz, C6H5), 129.5 (d, JC-P=2.2 Hz,
C6H5), 127.4 (d, JC-P=10.1 Hz, C6H5), 122.6 (d, JC-P=51.1 Hz,
C6H5), 108.9 (s, C6H4(p-cymene)), 94.1 (s, C6H4(p-cymene)), 90.4
(d, JC-P=4.2 Hz, C6H4(p-cymene)), 86.2 (d, JC-P=5.8 Hz, C6-
(s, NCH(CH3)2), 30.3 (s, CH(CH3)2(p-cymene)), 28.0 (d, JC-P
=
24.7 Hz, PCH(CH3)2), 22.6 (s, CH(CH3)2(p-cymene)), 21.6 (s,
NCH(CH3)2), 19.6 (d, JC-P = 35.2 Hz, PCH(CH3)2), 17.9 (s,
CH3(p-cymene)) ppm. 31P{1H} NMR (81.0 MHz, CDCl3): δ 74.5
ppm. DCI MS (CH4, positive mode): m/z 492 [M - p-cymene]+,
457 [M - Cl - p-cymene]+. IR (KBr): ν 2996 (w), 2964 (m), 2924
(m), 2869 (w), 1579 (m), 1558 (s), 1367 (m), 1321 (m), 1034 (m)
cm-1. Crystal data: see Supporting Information.
General Procedure for the Synthesis of Complexes 9a,b. A
solution of complex 8a (99 mg, 0.14 mmol) or 8b (58 mg, 0.09
mmol) in 5 mL of toluene was stirred at 80 °C for 20 h. An
orange precipitate was formed, the reaction mixture was al-
lowed to cool to room temperature, and the red surpernatant
solution was filtered off. The orange solid was dried under
vacuum to give respectively 85% (67 mg) and 70% (32 mg)
yields of 9a and 9b. Suitable crystals of 9a and 9b were obtained
from saturated dichloromethane solutions at -18 °C. 9a was
also obtained by stirring a solution of [(p-cymene)RuCl2]2 (85
mg, 0.139 mmol) and i-Pr2N-C(Ph)dN-PPh2 (7a) (108 mg,
0.278 mmol) in 5 mL of toluene at 80 °C for 20 h. 9a was isolated
in 72% yield.
H4(p-cymene)), 46.6 (s, NCH(CH3)2), 44.8 (s, NCH(CH3)2), 30.0
(s, CH(CH3)2(p-cymene)), 23.8 (s, NCH(CH3)2), 21.8 (s, CH-
(CH3)2(p-cymene)), 19.9 (s, NCH(CH3)2), 17.5 (s, CH3(p-cymene)
)
ppm. 31P{1H} NMR (81.0 MHz, CDCl3): δ 58.2 ppm. DCI MS
(CH4, positive mode): m/z 618 [M]+, 583 [M - Cl]+. IR (KBr): ν
3055 (w), 2973 (m), 2926 (w), 2870 (w), 2360 (w), 2341 (w), 1594
(s), 1569 (w), 1434 (m), 1403 (m), 1358 (m), 1295 (m), 1205 (m),
1103 (m), 888 (m), 835 (m), 703 (m), 697 (m), 527 (m) cm-1
Crystal data: see Supporting Information.
.
Computational Details
9a. Mp: 245-247 °C (dec). 1H NMR (300.1 MHz, CD2Cl2): δ
7.79-7.72 (m, 4H, C6H5), 7.42-7.39 (m, 6H, C6H5), 6.32 (m,
1H, η6-C6H5), 5.94 (t, 2H, JH-H=6.0 Hz, η6-C6H5), 5.26 (d, 2H,
Calculations were performed with the Gaussian 03 suite of
programs,27 using the density functional method.28 The hybrid
exchange functional B3LYP set was used. B3LYP29 is a three-
parameter functional developed by Becke that combines the
Becke gradient-corrected exchange functional and the Lee-
Yang-Parr and Vosko-Wilk-Nusair correlation functionals
with part of the exact HF exchange energy. All Gaussian
calculations were done in combination with the 6-31G** basis
set for C, P, N, Cl, and H (all atoms were augmented with a
J
NCH(CH3)2), 3.87 (sept, 1H, JH-H = 6.9 Hz, NCH(CH3)2),
H-H = 5.4 Hz, η6-C6H5), 4.13 (sept, 1H, JH-H = 6.6 Hz,
1.68 (d, 6H, JH-H=6.9 Hz, NCH(CH3)2), 1.29 (d, 6H, JH-H
=
6.6 Hz, NCH(CH3)2) ppm. 13C{1H} NMR (75.5 MHz, CD2Cl2):
δ 164.8 (d, JC-P=16.7 Hz, C(Ph)dN), 135.8 (d, JCP=59.8 Hz,
C6H5), 131.8 (d, JC-P=10.1 Hz, C6H5), 130.1 (d, JC-P=2.8 Hz,
C6H5), 127.6 (d, JC-P=11.0 Hz, C6H5), 122.2 (d, JC-P=6.4 Hz,
η6-C6H5), 95.7 (d, JC-P=3.8 Hz, η6-C6H5), 91.9 (d, JC-P=14.3
Hz, η6-C6H5), 75.0 (s, η6-C6H5), 55.8 (s, NCH(CH3)2), 48.1 (s,
NCH(CH3)2), 20.3 (s, NCH(CH3)2), 20.0 (s, NCH(CH3)2) ppm.
31P{1H} NMR (121.5 MHz, CD2Cl2): δ 75.9 ppm. DCI MS
(CH4, positive mode): m/z 560 [M]+, 525 [M - Cl]+. IR (KBr): ν
3057 (w), 2979 (w), 2934 (w), 1576 (m), 1558 (s), 1347 (m), 1034
(m), 699 (m), 539 (m) cm-1. Crystal data: see Supporting
Information.
(27) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T., Jr.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson,
G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, R.; Fukuda, J.;
Hasegawa, M.; Ishida, T.; Nakajima, Y.; Honda, O.; Kitao, H.; Nakai,
M. X.; Klene, X.; Li, K.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas,
D. K.; Malick, A. D.; Rabuck, K.; Raghavachari, J. B.; Foresman, J. V.;
Ortiz, Q.; Cui, A. G.; Baboul, S.; Clifford, O.; Cioslowski, J.; Stefanov,
B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.;
Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.;
Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.;
Gonzalez, C.; Pople, J. A. Gaussian 03, Revision D-02; Gaussian, Inc.:
Pittsburgh, PA, 2003.
9b. Mp: 149-151 °C. 1H NMR (300.1 MHz, CD2Cl2): δ 6.28
(td, JH-H=6.0 Hz and JH-P=1.2 Hz, 1H, η6-C6H5), 5.87 (t,
J
H-H=5.8 Hz, 2H, η6-C6H5),5.03(d, JH-H=5.6 Hz, 2H, η6-C6H5),
3.92 (sept, JH-H=6.6 Hz, 1H, NCH(CH3)2), 3.71 (sept, JH-H=
7.0 Hz, 1H, NCH(CH3)2), 2.49 (sept d, JH-H=7.0 Hz and JH-P=
9.2 Hz, 2H, PCH(CH3)2), 1.57 (d, JH-H=7.0 Hz, 6H, NCH-
(CH3)2, 1.29 (dd, JH-H = 6.9 Hz and JH-P = 14.7 Hz, 6H,
PCH(CH3)2), 1.21 (dd, JH-H=6.6 Hz and JH-P=10.0 Hz, 6H,
PCH(CH3)2), 1.22 (d, JH-H=6.6 Hz, 6H, NCH(CH3)2) ppm.
13C{1H} NMR (50.3 MHz, CD2Cl2): δ 164.9 (d, 2JCP=12.6 Hz,
(28) Parr R. G.; Yang W. Functional Theory of Atoms and Molecules;
Breslow, R., Goodenough, J. B., Eds.; Oxford University Press: New York, 1989.
(29) (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098. (b) Becke, A. D. J.
Chem. Phys. 1993, 98, 5648. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B
1988, 37, 785.
C(Ph)dN), 125.4 (d, JCP =6.0 Hz, η6-C6H5), 98.4 (d, JC-P
=
2.5 Hz, η6-C6H5), 89.3 (d, JC-P =13.6 Hz, η6-C6H5), 69.9 (s,
η6-C6H5), 55.9 (s, NCH(CH3)2), 48.2 (s, NCH(CH3)2), 28.5