Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide
K. E. Litz1, M. M. Banaszak Holl, J. W. Kampf
1Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055.
Abstract:
The reaction of (Et(3)P)(2)PtGe[N(SiMe(3))(2)](2) with dioxygen yields (Et(3)P)(2)Pt(&mgr;-eta(2)-O(2))Ge[N(SiMe(3))(2)](2) (1). Exposure of 1 to light resulted in a rearrangement to (Et(3)P)(2)PtO(2)Ge[N(SiMe(3))(2)](2) (2a), the first example of a bidentate, dianionic germanate ligand. The isomerization was judged to occur via an intramolecular O-O bond scission and rotation of the Pt-Ge bond. No free germylene was detected, and the reaction was found to be zero order. An analogue of 2a was prepared by direct reaction of (Ph(3)P)(2)PtO(2) with Ge[N(SiMe(3))(2)](2) yielding (Ph(3)P)(2)PtO(2)Ge[N(SiMe(3))(2)](2) (2b). Addition of SO(2) to 1 results in the formation of the bridging sulfate (Et(3)P)(2)Pt(&mgr;-eta(2)-SO(4))Ge[N(SiMe(3))(2)](2) (3). An infrared spectroscopy study of the sulfate reaction was performed using oxygen-18. The results indicate that direct insertion of SO(2) into the O-O bond does not occur. Formaldehyde was also observed to insert into the Pt-O bond of 1 giving (Et(3)P)(2)Pt(&mgr;-eta(2)-OCH(2)OO)Ge[N(SiMe(3))(2)](2) (5).
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