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5 (a) C. Li, M. Ogasawara, S. P. Nolan and K. G. Caulton,
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7 J. Espuelas, M. A. Esteruelas, F. J. Lahoz, L. A. Oro and C. Valero,
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41.
Complex 10. Yield: 0.13 g (97%). Calc. for C17H37ClO2P2-
RuS2: C, 38.0; H, 6.90. Found: C, 37.8; H, 6.98%. IR (Nujol,
cmϪ1): ν(CO) 1928. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.19–1.33 (m, 24 H, PCH(CH3)2), 1.43 (d, 6 H, JHP = 8.5 Hz,
PCH3), 2.20 and 2.40 (m, 2 H each, PCH(CH3)2) and 4.14 (s,
3 H, S2COCH3). 31P-{1H} NMR (161.89 MHz, CDCl3, 273 K):
δ 32.8 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 7.12
(m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.8 and 28.3
(m, PCH(CH3)2), 57.0 (s, S2COCH3), 199.2 (t, 2JCP = 2JCPЈ = 15.3
Hz, CO) and 230.9 (s, S2COCH3).
Complex 11. Yield: 0.13 g (94%). Calc. for C18H39ClO2P2-
RuS2: C, 39.3; H, 7.09. Found: C, 39.3; H, 7.19%. IR (Nujol,
cmϪ1): ν(CO) 1925. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.17–1.34 (m, 24 H, PCH(CH3)2), 1.42 (d, 6 H, JHP = 8.4,
PCH3), 2.16 and 2.38 (m, 2 H each, PCH(CH3)2), 1.41 (t, 3 H,
JCH ,CH = 7.2, S2COCH2CH3) and 4.59 (c, 2 H, JCH ,CH
=
2
2
3
7.2 3Hz, S2COCH2CH3). 31P-{1H} NMR (161.89 MHz, CDCl3,
273 K): δ 32.7 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3):
δ 7.12 (m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.8 and
28.2 (m, PCH(CH3)2), 13.8 (s, S2COCH2CH3), 66.9 (s, S2CO-
2
CH2CH3), 199.3 (t, JCP = 2JCPЈ = 15 Hz, CO) and 230.2 (s,
S2COCH2CH3).
Complex 12. Yield: 0.14 g (100%). Calc. for C19H41ClO2P2-
RuS2: C, 40.4; H, 7.27. Found: C, 41.1; H, 7.26%. IR (Nujol,
cmϪ1): ν(CO) 1936. 1H NMR (400 MHz, 293 K, CDCl3):
2
δ 1.17–1.34 (m, 24 H, PCH(CH3)2), 1.42 (d, 6 H, JHP = 8.4,
3
PCH3), 1.40 (d, 6 H, JCH ,CH = 6.4, S2COCH(CH3)2), 2.16 and
3
9 Y. Sun, N. J. Taylor and A. J. Carty, J. Organomet. Chem., 1992,
C43, 423; Organometallics, 1992, 11, 4293.
10 J. T. Poulton, M. P. Sigalas, O. Eisenstein and K. G. Caulton, Inorg.
Chem., 1993, 32, 5490; J. T. Poulton, M. P. Sigalas, K. Folting,
W. Streib, O. Eisenstein and K. G. Caulton, Inorg. Chem., 1994, 33,
1476.
11 R. Atencio, C. Bohanna, M. A. Esteruelas, F. J. Lahoz and
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12 M. L. Christ, S. Sabo-Etienne and B. Chaudret, Organometallics,
1994, 13, 3800.
3
2.38 (m, 2 H each, PCH(CH3)2) and 5.57 (sept, JCH,CH = 6.4
3
Hz, S2COCH(CH3)2). 31P-{1H} NMR (161.89 MHz, CDCl3,
273 K): δ 32.5 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3):
δ 7.1 (m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.9
and 28.2 (m, PCH(CH3)2), 21.8 (s, S2COCH(CH3)2), 75.6 (s,
2
S2COCH(CH3)2), 199.5 (t, JCP = 14 Hz, CO) and 229.7 (s,
S2COCH(CH3)2).
[RuCl(acac)(CO)(PiPr2Me)2] 13. To a solution of complex 1
(0.11 g, 0.25 mmol) in CH2Cl2 (5 ml) was added a suspension
formed by addition of potassium tert-butoxide (50 mg, 0.25
mmol) to 5 ml CH2Cl2–acetylacetone (1:1). The resulting
suspension was stirred for 12 h at room temperature and then
filtered through Celite. Removal of the solvent by vacuum
yielded a brown oil which was washed with Et2O. The oil sol-
idified at temperatures below Ϫ20 ЊC. Yield: 0.08 g (65%). Calc.
for C20H41ClO3P2Ru: C, 45.5; H, 7.77. Found: C, 45.1; H,
7.80%. IR (Nujol, cmϪ1): ν(CO) 1940, ν(COacac) 1590 and 1520.
1H NMR (400 MHz, 293 K, CDCl3): δ 1.04–1.31 (m, 30 H,
PCH(CH3)2 and PCH3), 2.15, 2.20, 2.61 and 2.68 (m, 2 H each,
PCH(CH3)2), 1.90 and 1.95 (s, 3 H each, CH3COCHCOCH3)
and 5.36 (s, 1 H, CH3COCHCOCH3). 31P-{1H} NMR (161.89
13 R. C. Mehrora, in Comprehensive Coordination Chemistry, eds.
G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon,
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3261.
14 D. Carmona, J. Ferrer, L. A. Oro, M. C. Apreda, M. C. C. Foces-
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15 C. K. Johnson, ORTEP, A Thermal Ellipsoid Plotting Program,
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16 M. A. Esteruelas, F. J. Lahoz, A. M. López, E. Oñate and L. A. Oro,
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19 I. de los Ríos, M. Jiménez-Tenorio, M. C. Puerta, I. Salcedo and
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20 G. Belchem, J. W. Steed and D. A. Tocher, J. Chem. Soc., Dalton
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22 A. Coto, M. Jiménez-Tenorio, M. C. Puerta and P. Valerga,
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23 W. Rigby, H. B. Lee, P. M. Bailey, J. A. McCleverty and P. M.
Maitlis, J. Chem. Soc., Dalton Trans., 1979, 387.
2
MHz, CDCl3, 273 K): δ 38.5 and 42.9 (d, JPPЈ = 26.3 Hz).
13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 6.26 and 6.68 (d,
1
1JCP = 26.6, JCPЈ = 25.8, PCH3), 17.4–19.0 (m, PCH(CH3)2),
24.6, 25.8, 26.1 and 26.3 (d, PCH(CH3)2), 25.5 and 28.0 (s,
CH3COCHCOCH3), 100.2 (s, CH3COCHCOCH3), 185.8 and
2
188.0 (s, CH3COCHCOCH3) and 204.2 (t, JCP = 2JCPЈ = 17.2
Hz, CO).
Acknowledgements
We thank Dra. Ma Ángeles Aramendía, from the Depart-
amento de Química Orgánica, Universidad de Córdoba, for
mass spectrometry measurements. Financial support from the
Ministerio de Educación y Ciencia of Spain (DGICYT, Project
PB97-1357) and Junta de Andalucía (PAI-FQM 0188) is
gratefully acknowledged. We thank Johnson Matthey plc for
generous loans of ruthenium trichloride.
24 M. A. Queirós and S. D. Robinson, Inorg. Chem., 1978, 17, 310.
25 P. T. Beurskens, DIRDIF, Technical Report 1984/1, Crystallography
Laboratory, Toernooiveld, 1984.
26 TEXSAN, Single-Crystal Structure Analysis Software, version 5.0,
Molecular Structure Corporation, Houston, TX, 1989.
References
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1 H. Werner, U. Meyer, M. A. Esteruelas, E. Sola and L. A. Oro,
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