Chloride labilization resulting from nucleophilic addition to cis-Ru(tpy)(CO)(2)Cl+PF6-: Synthesis and characterization of new CO2-bridged and formate complexes of ruthenium

被引:32
作者
Gibson, DH [1 ]
Sleadd, BA [1 ]
Mashuta, MS [1 ]
Richardson, JF [1 ]
机构
[1] UNIV LOUISVILLE,CTR CHEM CATALYSIS,LOUISVILLE,KY 40292
关键词
D O I
10.1021/om970493p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of cis-Ru(tpy)(CO)(2)Cl+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)(2)(2+)2PF(6)(-) (3). Reaction of 1 with aqueous NaOCHO yields the corresponding eta(1)-formato 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+)2PF(6)(-). 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 pi-acceptor ligand (CO) to a sigma-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)(2)Ru(CO2)Ru(tpy)(CO)(2)(2+)2PF(6)(-) (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.
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页码:4421 / 4427
页数:7
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