Synthesis and Reactivity of Zirconium Hydrazido Complexes Containing Aryloxide Ligation

Abstract:

The reaction of [(ArO)2Zr(Me)2] (ArO = 2,6-di-tert-butylphenoxide)with PhNHNHPh (1 equiv) leads to [(ArO)2Zr(Me)(η2-NPhNHPh)](1) and 1 equiv of methane. Heating a C6D6 solution of 1 generates [Zr{OC6H3(But)C(CH3)2CH}(OAr)(NPhNHPh)] (2) via cyclometalation of a tert-butyl group of the aryloxide ligand (1H NMR). Addition of 4-pyrrollidinopyridine (>2 equiv, py′) to 1 results in the formation of the η2-azobenzene complex [(ArO)2Zr(η2-N2Ph2)-(Py′)2] (3) with the elimination of methane. Solutions of 3 in C6D6 slowly convert to the terminal imido complex [(ArO)2Zr(═NPh) (py′)2] and free azobenzene. Reaction of 1 with organic isocyanides (1 equiv of RNC; R = But, 2,6-Me2C6H3) produces a mixed hydrazido, iminoacyl complex [(ArO)2Zr(η2-NPhNHPh)(η2-MeCNR)], R = But (4a), 2,6-Me2C6H3 (4b). Compound 4a crystallizes in space group P21/c with a = 19.666(5) Å, b = 12.166(3) Å, c = 19139(3) Å, β= 108.01(2)°, and Z = 4. The solid state structure of 4a shows both the hydrazido and iminoacyl groups to be η2-bound to the metal with an PhN—NHPh distance of 1.47(2) Á and ButN—CMe distance of 1.26(2) Å. © 1994, American Chemical Society. All rights reserved.

Año de publicación:

1994

Keywords:

Fuente:

scopus