Reactivity of Some Transition-Metal Systems toward Liquid Carbon Dioxide

Article abstract of DOI:10.1021/ja00383a026

The reactivity of several transition-metal complexes toward liquid CO2 has been investigated as a means of screening such complexes for their ability to bind CO2.Although the known Ni(CO2)(PCy3)2 complex was prepared by the reaction of 2(μ-N2) with CO2(l), the compounds Pd(PCy3)2 and Pt(PCy3)2 do not react with CO2(l) to afford CO2 complexes.But the compound Pt(PCy3)2 does react with wet CO2 to afford PhH(O2COH)(PCy3)2, a bicarbonato complex.Similar reactivity was seen for W(CO)3(PCy3)2, which produces WH(O2COH)(CO)3(PCy3)2 in wet CO2(l).The compounds Na and 2(μ-N2) react with CO(l) to form complexes that contain carbonyl and carbonato ligands.Peroxocarbonato complexes, IrR(OCO3)(CO)(PPh3)2 (R = Me, Ph), were prepared from IrR(O2)(CO)(PPh3)2 with CO2(l).