195719-82-5Relevant academic research and scientific papers
Chloride labilization resulting from nucleophilic addition to cis-Ru(tpy)(CO)2Cl+PF6-: Synthesis and characterization of new CO2-bridged and formate complexes of ruthenium
Gibson, Dorothy H.,Sleadd, Bradley A.,Mashuta, Mark S.,Richardson, John F.
, p. 4421 - 4427 (1997)
Reaction of cis-Ru(tpy)(CO)2Cl+PF6- (1; tpy = 2,2′:6′,2″-terpyridyl) with aqueous Na2CO3 in acetonitrile yields the CO2-bridged complex cis,cis-(CH3CN)(CO)(tpy)Ru(CO2)Ru(tpy)-(CO) 22+2PF6- (3). Reaction of 1 with aqueous NaOCHO yields the corresponding η1-formate complex 4; reaction of 4 with aqueous Na2CO3 also provides 3. Reaction of 3 with CO results in displacement of acetonitrile and formation of 5, cis,cis-(CO)2(tpy)Ru(CO2)Ru(tpy)(CO)2 2+2PF6-. Reaction paths leading to 3 and 4 from 1 are thought to occur by base-assisted trans labilization of chloride resulting from conversion of a π-acceptor ligand (CO) to a σ-donor (COOH). Support for proposed steps in the reaction paths leading to 3 and 4 was provided by a trapping experiment in which 1 reacts with cis-Ru(bpy)2(CO)COOH+PF6- in the presence of aqueous Na2CO3 to give cis,cis-(CO)(bpy)2Ru(CO2)Ru(tpy)(CO)2 2+2PF6- (7; bpy = 2,2′-bipyridyl), which has been structurally characterized. Parallels between these reactions and the halide labilizations which occur with ruthenium or rhenium polypyridyl complexes during photochemical or electrochemical reductions of CO2 are discussed.
