Cis-Bisphenylalkynyl cyclodiphosphazane: Oxidation reactions and transition metal complexes

Abstract

The oxidation reactions and transition metal complexes of cis-bisphenylalkynyl cyclodiphosphazane [cis-(PhC≡CP)2(μ-NtBu)2] (1) is described. The reaction of 1 with aq. H2O2 and elemental selenium afforded bischalcogenides [cis-(PhC≡CPO)2(μ-NtBu)2] (3) and [cis-(PhC≡CPSe)2(μ-NtBu)2] (4). Treatment of 1 with [Ru(η6-p-cymene)Cl2]2 and [{Pd(η3-C3H5)Cl}2] yielded dinuclear complexes [{Ru(p-cymene)Cl2}2{cis-(PhC≡CP)2(μ-NtBu)2}] (5) and [{PdCl(η3-C3H5)}2{cis-(PhC≡CP)2(μ-NtBu)2}] (6). Mixed ligand complexes [{(2,2′-bpy)CuI}2{cis-(PhC≡CP)2(μ-NtBu)2}] (7) and [{(1,10-phen)CuI}2{cis-(PhC≡CP)2(μ-NtBu)2}] (8) were obtained by reacting 1 with CuI followed by the addition of 2,2′-bipyridine and 1,10-phenanthroline, respectively. Treatment of 1 and [trans-(PhC≡CP)2(μ-NtBu)2] (2) with [AuCl(SMe2)] afforded dinuclear complexes [(AuCl)2{cis-(PhC≡CP)2(μ-NtBu)2}] (9) and [(AuCl)2{trans-(PhC≡CP)2(μ-NtBu)2}] (10), respectively, in good yields. Both the complexes 9 and 10 exhibit intermolecular aurophilic interactions. The X-ray analysis showed dimeric structure for 9, whereas 10 consists of a 1D-polymeric structure, due to aurophilic interactions. The crystal structures of 5, 9 and 10 were established by X-ray diffraction analysis.