Issue 12, 2015

Why are the {Cu4N4} rings in copper(i) phosphinimide clusters [Cu{μ-N[double bond, length as m-dash]PR3}]4 (R = NMe3 or Ph) planar?

Abstract

The copper phosphinimide complexes [Cu{μ-N[double bond, length as m-dash]PR3}]4 (1, R = NMe2 and 2, R = Ph) were obtained in good yields from the reactions of Cu[Mes] (Mes = mesityl, C6H2Me3-2,4,6) with the corresponding iminophosphoranes, HNPR3. The molecular structures of 1 and 2 reveal the presence of planar eight-membered {Cu4N4} rings which contrasts with the saddle-shaped {M4N4} rings found in related metal phosphinimide complexes. According to computations, there is negligible aromaticity in the planar {Cu4N4} rings in 1 and 2 and the saddle shape observed in related {M4N4} rings is due to steric factors.

Graphical abstract: Why are the {Cu4N4} rings in copper(i) phosphinimide clusters [Cu{μ-N [[double bond, length as m-dash]] PR3}]4 (R = NMe3 or Ph) planar?

Supplementary files

Article information

Article type
Paper
Submitted
19 Jan 2015
Accepted
12 Feb 2015
First published
12 Feb 2015
This article is Open Access
Creative Commons BY license

Dalton Trans., 2015,44, 5611-5619

Author version available

Why are the {Cu4N4} rings in copper(I) phosphinimide clusters [Cu{μ-N[double bond, length as m-dash]PR3}]4 (R = NMe3 or Ph) planar?

T. P. Robinson, R. D. Price, M. G. Davidson, M. A. Fox and A. L. Johnson, Dalton Trans., 2015, 44, 5611 DOI: 10.1039/C5DT00255A

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