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Issue 26, 2012
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Synthesis of U(iv) imidos from Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by extrusion of bibenzyl

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Abstract

Addition of organic azides, N3R (R = 2,4,6-trimethylphenyl (Mes), phenyl (Ph), 1-adamantyl (Ad)), to a solution of the uranium(III) alkyl complex, Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) (1), results in the formation of a family of uranium(IV) imido derivatives, Tp*2U(NR) (2-R). Notably, these complexes were synthesized in high yields by coupling of the benzyl groups to form bibenzyl. The uranium(IV) imido derivatives, 2-Mes, 2-Ph, and 2-Ad, were all characterized by both 1H NMR and IR spectroscopy, and 2-Mes and 2-Ad were also characterized by X-ray crystallography. In the molecular structure of 2-Mes, typical κ3-coordination of the Tp* ligands was observed; however in the case of 2-Ad, one pyrazole ring of a Tp* ligand has rotated away from the metal centre, forcing a κ2-coordination of the pyrazoles. This results in a uranium–hydrogen interaction with the Tp* B–H. Treating these imido complexes with para-tolualdehyde results in multiple bond metathesis, forming the terminal uranium(IV) oxo complex, Tp*2U(O), and the corresponding imine.

Graphical abstract: Synthesis of U(iv) imidos from Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by extrusion of bibenzyl

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Supplementary files

Article information


Submitted
17 Dec 2011
Accepted
01 Mar 2012
First published
04 Apr 2012

Dalton Trans., 2012,41, 7952-7958
Article type
Paper

Synthesis of U(IV) imidos from Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by extrusion of bibenzyl

E. M. Matson, M. G. Crestani, P. E. Fanwick and S. C. Bart, Dalton Trans., 2012, 41, 7952
DOI: 10.1039/C2DT12439D

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