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Structures and Reactivity of Zr(IV) Chlorobenzene Complexes

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posted on 2004-12-01, 00:00 authored by Fan Wu, Aswini K. Dash, Richard F. Jordan
The synthesis, structures, and unusual reactivity of (C5R5)2ZrR‘(ClPh)+ chlorobenzene complexes are described. The reaction of (C5R5)2ZrR‘2 with [Ph3C][B(C6F5)4] in C6D5Cl affords [(C5R5)2ZrR‘(ClC6D5)][B(C6F5)4] chlorobenzene complexes (1-d5, R‘ = CH2Ph and (C5R5)2 = (C5H5)2; 2ad-d5, R‘ = Me and (C5R5)2 = rac-(1,2-ethylene(bis)indenyl) (2a), (C5H5)2 (2b), (C5H4Me)2 (2c), (C5Me5)2 (2d, C5Me5 = Cp*)). Complexes 1 and 2b,c are thermally robust but are converted to [{(C5R5)2Zr(μ-Cl)}2][B(C6F5)4]2 (4b,c) by a photochemical process in ClPh solution. In contrast, 2d undergoes facile thermal ortho-C−H activation to yield [Cp*2Zr(η2-C,Cl-2-Cl-C6H4)][B(C6F5)4] (5), which slowly rearranges to [(η4,η-C5Me5C6H4)Cp*ZrCl][B(C6F5)4] (6) via β-Cl elimination and benzyne insertion into a Zr−CCp* bond. The higher thermal reactivity of 2d versus that of 1 and 2b,c is attributed to steric crowding associated with the Cp* ligands of 2d, which forces a ClPh ortho-hydrogen close to the Zr−Me group.