Organometallics p. 1793 - 1803 (1996)
Update date:2022-09-26
Topics: Synthesis X-ray crystal structures Cl CO Insertion Catalytic Reactions PPH3 Experimental terms Coordinatively unsaturated
Maddock, Susan M.
Rickard, Clifton E. F.
Roper, Warren R.
Wright, L. James
The five-coordinate silyl complexes Ru(SiR3)Cl(CO)(PPh3)2(R3 = Me3 (1a), Et3 (1b), Ph3 (1c), Me2Cl (1f)) are conveniently prepared through reaction of Ru(Ph)Cl(CO)(PPh3)2 with the appropriate silane, HSiR3. Reaction of the Si-Cl bond in 1f with ethanol or hydroxide gives the corresponding ethoxysilyl or hydroxysilyl products Ru(SiMe2X)Cl(CO)(PPh3)2 (X = OEt (1d), OH (1e)). Ethyne readily inserts into the Ru-Si bond of 1a-d, and the corresponding five-coordinate, silylalkenyl complexes Ru(CH=CHSiR3)Cl(CO)(PPh3)2 (R3 = Me3 (2a), Et3 (2b), Ph3 (2c), Me2OEt (2d)) can be isolated in good yield. The complexes Ru(CH=CHSiR3)Cl(CO)2(PPh3)2 (SiR3 = SiMe3 (3a), SiEt3 (3b), SiMe2OEt (3d)) result from carbonylation of 2a,b,d. An X-ray crystal structure determination of Ru(CH=CHSiMe2-OEt)Cl(CO)2(PPh3)2 (3d) has been obtained. Reaction of Ru(CH=CHSiMe3)Cl(CO)(PPh3)2 (2a) with CN-p-tolyl or sodium acetate gives Ru(CH=CHSiMe3)Cl(CO)(CN-p-tolyl)(PPh3)2 (4a) or Ru(CH=CHSiMe3)(η2-O2CCH 3)(CO)(PPh3)2 (5a), respectively. Insertion of ethyne into the Ru-Si bond of 1e results in the formation of the metallacyclic ring-containing complex, Ru(CH=CHSiMe2OH)Cl(CO)(PPh3)2 (6e), in which the hydroxysilyl oxygen atom is coordinated to ruthenium. Reaction of 6e with AgClO4 gives [Ru(CH=CHSiMe2OH)(CO)-(NCMe)(PPh3)2]ClO 4 (7e) and substitution of the labile acetonitrile in this compound with CO or CN-p-tolyl generates [Ru(CH=CHSiMe2OH)(CO)2(PPh3) 2]ClO4 (8e) or [Ru(CH=CH-SiMe2OH)(CO)(CN-p-tolyl)(PPh3) 2]ClO4 (9e), respectively. The crystal structure of 9e has been determined. Deprotonation of 8e or 9e with KOH gives the neutral complexes Ru-(CH=CHSiMe2O)(CO)2(PPh3)2 (10e) or Ru(CH=CHSiMe2O)(CO)(CN-p-tolyl)(PPh3)2 (11e), respectively. Complex 1b has been shown to catalyze the hydrosilylation of both ethyne and phenylethyne by HSiEt3.
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Doi:10.1016/0040-4020(95)01105-6
(1996)Doi:10.1039/cc9960000253
(1996)Doi:10.1016/0277-5387(95)00406-8
(1996)Doi:10.1021/ja00189a007
(1989)Doi:10.1039/FT9969200377
(1996)Doi:10.1021/jo01276a037
(1968)
