82728-97-0Relevant articles and documents
Synthesis and reactivity of pentamethylcyclopentadienyl ruthenium formyl and α-hydroxy complexes
Nelson, Gregory O.,Sumner, Charles E.
, p. 1983 - 1990 (2008/10/08)
The transition-metal complexes - (η-C5Me5)Ru(CO)2CH2OH (7), (η-C5Me5)Ru(CO)2CHO (10), and (η-C5Me5)Ru(CO)(PMe2Ph)CHO (11) - were synthesized and studied as models for intermediates thought to be involved in the reduction of CO to organic oxygenates by transition-metal catalysts. Complex 7 was prepared by NaBH3CN reduction of (η-C5Me5)Ru(CO)3+BF 4- (1). Compound 10 was synthesized by reduction of 1 with [Ph3PCuH]6, but it could not be isolated in pure form. Pure crystalline 11 was isolated from the reduction of (η-C5Me5)Ru(CO)2(PMe2Ph) +I- (2) with NaBH4 in tetrahydrofuran/water. Formyl complexes 10 and 11 were shown to decompose by radical chain mechanism as evidenced by the fact that the addition of 9,10-dihydroanthracene, a hydrogen atom donor, to solutions of 10 or 11 drastically slowed their decomposition. The intermediate formed from the decomposition of 11 was shown to undergo electron transfer with (η-C5R5)Ru(CO)2I (R = H, Me). An X-ray structure of 11 was completed.
