Synthesis and Structure of Donor-Ligand-Stabilized Tris(cyclopentadienyl)zirconium Cations

Abstract

Treatment of Cp 2 Zr(Cl)CH 3 ( 6 ) with sodium cyclopentadienide gives Cp 3 ZrCH 3 ( 7 ). Its reaction with dimethylanilinium tetraphenylborate yields the Cp 3 Zr(THF) + cation. [Cp 3 Zr + CH 3 B(C 6 F 5 ) 3 - ] ( 9 ) is generated by treatment of 7 with tris(pentafluorophenyl)borate. Nitriles add to 9 to form the ligand-stabilized tris(η 5 -cyclopentadienyl)zirconium cation systems Cp 3 Zr(N⋮CR) + . With tert -butyl isocyanide, 9 is transformed to yield the donor-ligand-stabilized [Cp 3 Zr(C⋮NCMe) 3 + CH 3 B(C 6 F 5 ) 3 - ] salt 12 . Carbon monoxide adds to 9 to give the cationic metal carbonyl complex [Cp 3 Zr(CO) + CH 3 B(C 6 F 5 ) 3 - ] ( 13 ). Both cation complexes 12 and 13 were characterized by X-ray diffraction.