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Issue 12, 2015
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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?

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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?

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Publication details

The article was received on 19 Jan 2015, accepted on 12 Feb 2015 and first published on 12 Feb 2015


Article type: Paper
DOI: 10.1039/C5DT00255A
Citation: Dalton Trans., 2015,44, 5611-5619
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    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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