The reactivity of the dinuclear halo-bridged cycloplatinated complex [Pt(μ-Cl){(κ2-P,C)P(OC6H4)(OPh)2}]2 towards neutral ligands

The reactivity of (cis- + trans-)[Pt(μ-Cl){(κ2-P,C)P(OC6H4)(OPh)2}]2 (1) towards several ligands L (L = RCN, P(OMe)3, DMSO, NHEt2, py, CO, C2H4, C8H16) has been studied. Ethylene and 1-octene do not react while the other reactions proceed with cleavage of the halide bridge and formation of one or both geometrical isomers of [PtCl{(κ2-P,C)P(OC6H4)(OPh)2}L] (2–8) depending on the nature of the entering ligand. In some cases equilibrium reactions (L = RCN, DMSO, CO, py) were observed. The structures of [SP4-3]-[PtCl{(κ2-P,C)P(OC6H4)(OPh)2}(S)DMSO] ([SP4-3]-4) and [SP4-4]-[[PtCl{(κ2-P,C)P(OC6H4)(OPh)2}py] ([SP4-4]-6) are reported.

Graphical abstractThe reactivity of (cis- + trans-)[Pt(μ-Cl){(κ2-P,C)P(OC6H4)(OPh)2}]2 towards several ligands (RCN, P(OMe)3, DMSO, NHEt2, py, CO, C2H4, C8H16) has been studied.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► [Pt(μ-Cl){(κ2-P,C)P(OC6H4)(OPh)2}]2 reacts with neutral nucleophiles. ► Reaction products may revert to the reagent under vacuum depending on the ligand. ► Stability of the products under vacuum follows the order RCN < CO < DMSO < py. ► Products with L = NHEt2, P(OMe)3 are thermally resistant under vacuum. ► π-Acid ligands prefer a coordination trans to the metallated carbon.