Reactions Of Platinum Complexes With Dimethylamine Borane PDF Download

This thesis describes a study of the reactions of platinum complexes with dimethylamine-borane (DMAB) as models for alkane activation. It is concluded that sigmaborane complexes of platinum(II) or platinum(IV) will be difficult to synthesize or even to detect as intermediates in hydride transfer from boranes to platinum. The complex [PtMe(O2CCF3)(bpy)] reacts with DMAB to form an intermediate [PtMeH(bpy)] complex, which undergoes reductive elimination of methane with further degradation to give platinum(0) and free 2,2'-bipyridine. The addition of methyl acrylate to the reaction allowed the trapping of the platinum-hydride, producing [PtCl(CHMeCO2Me)(bpy)] and [Pt(CHMeCO2Me)2(bpy)]. Oxidative addition of methyl iodide produced the complex [PtMe(CHMeCO2Me)Cl(I)(bpy)]. As well, the reaction of [Pt(O2CCF3)2(dppe)] with DMAB afforded the [Pt( -H)(dppe)]2[O2CCF3]2 complex. These complexes are characterized by NMR spectroscopy, with additional structural information obtained from the crystal structure of [PtMe(CHMeCO2Me)Cl(I)(bpy)]. Complexes [PtMe3(OTf)(bpy)] and [PtMe3(OTf)(bu2bpy)] react with DMAB to afford [PtMe3(Me2NH)(bpy)]+, [Pt2Me6( -H)(bpy)2]+, [PtMe3(Me2NH)(bu2bpy)]+, and [Pt2Me6( -H)(bu2bpy)2]+. The addition of dibenzoyl peroxide to [PtMe2(bpy)] yielded [PtMe2(OBn)2(bpy)]. The reaction of [PtMe3(OTf)(dmpe)] with DMAB afforded the [PtMe4(dmpe)] complex. These complexes are characterized by NMR spectroscopy.