Dinuclear Cationic Zirconium Hydrides Stabilized by the N,N-Dibenzylcyclam Ancillary Ligand

resumo

The reaction of [Bn(2)Cyclam]ZrCl2 (Bn = benzyl) with 2 equiv of KHBEt3 generates the ionic dinuclear zirconium derivative [([Bn(2)Cyclam]Zr)(2)(mu-H)(3)] [(Et3B)(2)H]. An analogous trihydride is obtained when [Bn(2)Cyclam]Zr(CH2Ph)(2) reacts with BEt3 in the presence of dihydrogen, whereas in the absence of BEt3, the bis(ortho-metalated) derivative [(C6H4CH2)(2)Cyclam]Zr is obtained. DFT calculations support the stability of a cationic dinuclear trihydride complex in comparison to the neutral dinuclear tetrahydride.

palavras-chave

CARBON-MONOXIDE; ASYMMETRIC HYDROGENATION; ZIRCONOCENE HYDRIDES; HAFNIUM COMPLEXES; ORGANIC-SYNTHESIS; ALKYL COMPLEXES; DERIVATIVES; REACTIVITY; REDUCTION; HYDROZIRCONATION

categoria

Chemistry

autores

Munha, RF; Ballmann, J; Veiros, LF; Patrick, BO; Fryzuk, MD; Martins, AM

nossos autores

Grupos

agradecimentos

M.D.F. thanks NSERC of Canada for a Discovery Grant. A.A.M. and R.F.M. thank the Fundacao para a Ciencia e Tecnologia for funding. We thank Nathan Halcovitch for his assistance with the diffraction experiments.

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