High-yield syntheses of the novel cations cis-Ru(N-N)(eta (2)-tpy)(CO)(2)(2
+)2PF(6)(-) (2a,b: N-N = 2,2'-bipyridine, tpy = 2,2':6',2 " -terpyridine; 5
a,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+)2PF(6)(
-) (9) with the appropriate bipyridine. Their linkage isomers, 2b and 5b, a
re produced by thermolysis of 2a and 5a. Procedures are described for the s
odium 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 possi
ble intermediacy of some of these compounds in catalytic reductions of CO2
leading to glyoxylic or glycolic acid is discussed.