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Free keywords:
CARBON-FLUORINE BONDS; INTERMOLECULAR C-F; CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURE; ETA-4-HEXAFLUOROBENZENE COMPLEXES; METAL-COMPLEXES; SOLID-STATE; ACTIVATION; HEXAFLUOROBENZENE; BENZENE
Abstract:
Thermolysis of (tBu2PC2H4PtBu2)NiMe2 in benzene or reduction of (tBu2PC2H4PtBu2)NiCl2 with Mg* in THF/benzene affords a solution of mononuclear (tBu2PC2H4PtBu2)Ni(η2-C6H6) (1) and dinuclear {(tBu2PC2H4PtBu2)Ni}2(μ-η2:η2-C6H6) (2) in equilibrium. Complex 2 has been isolated; the X-ray structure analysis reveals an antifacial coordination of the [(tBu2PC2H4PtBu2)Ni0] moieties to adjacent CC bonds of a formal cyclohexatriene ligand. According to solid-state and solution NMR the structure of 2 is static in the solid and fluxional in solution. Displacement of the benzene ligand in 1 or 2 by C6F6 affords mononuclear (tBu2PC2H4PtBu2)Ni(η2-C6F6) (5) for which the molecular structure is also reported.