Dispersion-Force-Assisted Disproportionation: A Stable Two-Coordinate Copper(II) Complex

Clifton L Wagner; Lizhi Tao; Emily J Thompson; Troy A Stich; Jingdong Guo; James C Fettinger; Louise A Berben; R David Britt; Shigeru Nagase; Philip P Power

doi:10.1002/anie.201605061

Dispersion-Force-Assisted Disproportionation: A Stable Two-Coordinate Copper(II) Complex

Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10444-7. doi: 10.1002/anie.201605061. Epub 2016 Jul 15.

Authors

Affiliations

¹ Department of Chemistry, University of California, Davis, One Shield Avenue, Davis, CA, 95616, USA.
² Fukui Institute for Fundamental Chemistry, Kyoto University, Takano Nishi-Hiraki-cho, 34-4, Sakyo-ku, Kyoto, 606-8103, Japan.
³ Department of Chemistry, University of California, Davis, One Shield Avenue, Davis, CA, 95616, USA. pppower@ucdavis.edu.

PMID: 27416899
DOI: 10.1002/anie.201605061

Abstract

The synthesis of the first linear coordinated Cu(II) complex Cu{N(SiMe3 )Dipp}2 (1 Dipp=C6 H5 -2,6Pr(i) 2 ) and its Cu(I) counterpart [Cu{N(SiMe3 )Dipp}2 ](-) (2) is described. The formation of 1 proceeds through a dispersion force-driven disproportionation, and is the reaction product of a Cu(I) halide and LiN(SiMe3 )Dipp in a non-donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15-crown-5. EPR spectroscopy of 1 provides the first detailed study of a two-coordinate transition-metal complex indicating strong covalency in the Cu-N bonds.

Keywords: EPR spectroscopy; copper; dispersion effects; disproportionation; silylamide.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.