Abstract
Abstract Reactions between square planar complexes, trans-Ir(CO)(R)L2 (R = Cl, Me; L = PPh3, P(p-tolyl)3, PMePh2), trans-Pt(Cl)(H)L2 (L′ = PPh3, P(p-tolyl)3, PEt3), cis-Pt(Cl)2L′2 and trans-Pt(Cl)2(PEt3)2, result in intermolecular exchange of phosphine ligands. Exchange between two iridium complexes is facile; exchanges between iridium and platinum complexes or between two platinum complexes occur with half-lives of hours. The reactions are followed by 31P NMR. The reactions are best interpreted as phosphine ligand dissociation with dissociation from iridium occurring more readily than from platinum. The observed phosphine dependence on the rate, L = P(p-tolyl)3 > PPh3 > PEt3 is consistent with a dissociative process. The dissociated phosphine then causes an associative substitution with the other complexes. Associative substitution on square planar iridium(I) complexes are known to occur much more readily than on square planar platinum(II) complexes.
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