Synthesis and Characterization of Formyl and Hydroxymethyl Complexes Derived from Isomeric Cations:  cis-Ru(N−N)(η2-tpy)(CO)2 2+2PF6 - (N−N = 2,2‘-Bipyridine, 4,4‘-Dimethyl-2,2‘-bipyridine; tpy = 2,2‘:6‘,2‘ ‘-Terpyridine)

• Published in: Organometallics 2001-11, Vol.20 (23), p.4956-4964
• Main Authors: Gibson, Dorothy H, Andino, Jose G, Bhamidi, Srinivas, Sleadd, Bradley A, Mashuta, Mark S
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om010520i

High-yield syntheses of the novel cations cis-Ru(N−N)(η2-tpy)(CO)2 2+2PF6 - (2a,b:  N−N = 2,2‘-bipyridine, tpy = 2,2‘:6‘,2‘ ‘-terpyridine; 5a,b:  N−N = 4,4‘-dimethyl-2,2‘-bipyridine) have been developed. Compounds 2a and 5a are produced from reactions of cis-Ru(tpy)(CO)2(CH3CN)2+2PF6 - (9) with the appropriate bipyridine. Their linkage isomers, 2b and 5b, are produced by thermolysis of 2a and 5a. Procedures are described for the sodium borohydride reductions of 2a,b and 5a,b to the corresponding formyl (3a,b and 6a,b) and hydroxymethyl (4a,b and 7a,b) derivatives. Compounds 2a, 2b, 5b, and 4a have been characterized by X-ray crystallography. The possible intermediacy of some of these compounds in catalytic reductions of CO2 leading to glyoxylic or glycolic acid is discussed.