Proton-induced cis-trans conversion of a platinum(II) center coordinated by L-cysteinatocobalt(III) metalloligands

Treatment of LambdaL-Co(L-cys-N,S)(en)2]+ (l-H2cys = L-cysteine) with PtCl4]2- in water, followed by the addition of acid, gave an S-bridged CoIII2PtII trinuclear complex (1]4+), which was reversibly converted to its deprotonated complex (2]2+) in an aqueous solution. While 1]4+ formed only a trans isomer, 2]2+ existed as a mixture of trans and cis isomers. The selective formation of a cis isomer was achieved by treatment of 1]4+ or 2]2+ with phthalic acid in water, which afforded a unique CoIII4PtII2 hexanuclear complex (3]4+). Complex 3]4+ was reverted back to 1]4+ by treatment with aqueous HCl, accompanied by the complete cis-to-trans conversion.