Master of Science
Dr. R.J. Puddephatt
This thesis describes a study of the reactions of platinum complexes with dimethylamine-borane (DMAB) as models for alkane activation. It is concluded that sigma-borane 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(µ-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(µ-H)(bpy)2]+, [PtMe3(Me2NH)(bu2bpy)]+, and [Pt2Me6(µ-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.
Robinson, Shawn M., "Reactions of Platinum Complexes with Dimethylamine-borane" (2012). Electronic Thesis and Dissertation Repository. 776.