Bis(triphenylphosphine)carbonatoplatinum(II)

Abstract

FURTHER studies on what was believedl by analogy with the carbon disulphide and carbonyl sulphide complexes, e.g., (Ph3P)2PtCS2,1~2 to be a carbon dioxide complex have shown that, in fact, in the complete absence of oxygen (or air), tris(triphenylphosphine)platinum(O) in diethyl ether or benzene solution does not react with carbon dioxide at 25'. On admission of oxygen, a rapid reaction occurs and white to pale yellow crystals of a hitherto unknown type of carbonate-complex, (Ph,P),PtCO, are precipitated according to the stoicheiometric equation :

Reactions of dioxygen complexes of nickel and palladium

“…When the reactant is an electrophile, the reduction in electron density in metal (hence in the dioxygen ligand) would not favor the 0-0 bond cleavage. Indeed we observed retention of the 0-0 bond upon the attack of an electrophile (eq [13][14][15]). An extreme case is the attack of a halogen molecule which results in a complete reverse flow of electronic populations from a dioxygen ligand to the reagent.…”

Carbonatobis(triphenylphosphine)platinum(II) benzene solvate: a redetermination

“…Earlier studies have shown that tris(triphenylphosphine)platinum does not react with carbon dioxide in the absence of oxygen; however, in the presence of O 2 , a rapid reaction occurs (Nyman et al, 1967). We have found that tetrakis(triphenylphosphine)platinum reacts in C 6 D 6 with air to give carbonatobis(triphenylphosphine)platinum(II), (I), as shown in the reaction scheme below.…”