Binuclear Organoplatinum(IV) Complexes with Bridging Xylenediyl Groups: Formation of Supramolecular Polymers through Hydrogen Bonding

Oxidative addition reactions of α,α′-dibromo-o-xylene, -m-xylene, and -p-xylene to two units of [PtMe2(bu2bipy)], bu2bipy = 4,4′-di-t-butyl-2,2′-bipyridine, give the corresponding binuclear organoplatinum(IV) complexes with bridging xylenediyl groups, [C6H4{CH2PtBrMe2(bu2bipy)}2]. Oxidative addition of C6-1,3,5-Me3-2,4,6-(CH2Br)3 to three units of [PtMe2(bu2bipy)] gave the triplatinum(IV) complex [C6-1,3,5-Me3-2,4,6-{CH2PtBrMe2(bu2bipy)}2]. In the sterically congested complexes 1,2-[C6H4{CH2PtBrMe2(bu2bipy)}2] and [C6-1,3,5-Me3-2,4,6-{CH2PtBrMe2(bu2bipy)}2], there is restricted rotation of the xylylplatinum groups. Bromide abstraction from the binuclear bromoplatinum(IV) complexes with AgPF6, followed by the addition of a pyridine ligand with one or two carboxylic acid functional groups, gave binuclear organoplatinum(IV) compounds containing at least two carboxylic acid groups, with the potential to polymerize through intermolecular hydrogen-bonding interaction in the solid state. During crystallization o...