Bismuth(III) halides as halide source for preparation of dihaloplatinum(IV) complexes

The complexes [PtMe2(tBu2bpy)], 1a, tBu2bpy = 4,4′-di-tert butyl-2,2′-bipyridine, and [PtMe(ppy)PPh3], 1b, ppy = deprotonated 2-phenylpyridine, react very easily with BiX3 (X = Cl, Br, or I) to give [PtMe2(X)2(tBu2bpy)] (2a, X = Cl; 3a, X = Br; 4a, X = I) and [PtMe(X)2(ppy)PPh3] (2b, X = Cl; 3b, X = Br; 4b, X = I), respectively. In these oxidative addition reactions, BiX3 reagent can be used as halide source instead of hazardous reagents X2. The dihaloplatinum(IV) complexes are characterized using NMR spectroscopy and the structures of complexes 4a and 3b are further identified by X-ray crystallography. Structures of Pt(IV) complexes are investigated using DFT calculations at B3LYP level of theory.

Graphical abstractBismuth trihalides, instead of hazardous reagents X2, were used as halide source for synthesis of dihaloplatinum(IV) complexes.Figure optionsDownload full-size imageDownload as PowerPoint slide