Diverse C−C Bond-Forming Reactions of Bis(carbene)platinum(II) Complexes

Abstract

The platinum(0) complex Pt(PPh_3)_4 catalyzes coupling of the carbene ligands of (CO)_5Cr{C(OMe)(p-MeOC_6H_4)} (1). The stable bis(carbene)platinum(II) complexes Cl_2Pt{C(OMe)(Me)}_2 (3), Br_2Pt{C(OMe)(Me)}_2 (4), and Cl_2Pt{C(O^iPr)(Me)}_2 (5) can be induced to undergo C–C coupling reactions by several means. Reduction of 3–5 to platinum(0) with cobaltocene results in formation of internal olefins, (E/Z)-2,3-dimethoxybut-2-ene (6) or (E/Z)-2,3-diisopropoxybut-2-ene (7). Reaction of 3–5 with PPh3 yields terminal olefins, 2,3-dimethoxybut-1-ene (13) or 2,3-diisopropoxybut-1-ene (15), along with Cl_2Pt(PPh_3)_2 (12) or Br_2Pt(PPh_3)_2 (14). In contrast, addition of pyridine to 3–5 does not effect C–C coupling; instead, the acyl complexes cis-Cl(py)Pt(COMe){C(OMe)(Me)} (8), cis-Br(py)Pt(COMe){C(OMe)(Me)} (9), and cis-Cl(py)Pt(COMe){C(O^iPr)(Me)} (10) are obtained, with concomitant formation of alkyl halide. Possible mechanistic pathways for C–C bond formation are discussed, as well as explanations for the different reactivities observed for pyridine and PPh_3.

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