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Issue 29, 2010
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Sm(ii)reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitriles

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Abstract

Reactions of a dimetallated N,N′-dimethyl substituted porphyrinogen Sm(II) complex with a series of t-butyl substituted heteroalkynes affords a diverse range of reactivity. The phosphaalkyne t-BuC[triple bond, length as m-dash]P gives a dinuclear Sm(III) P–P reductively coupled complex of (t-BuC[double bond, length as m-dash]PP[double bond, length as m-dash]C-t-Bu)2− featuring a new μ-η2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuC[triple bond, length as m-dash]N forms Sm(II) adducts that undergo reductive C–C bond cleavage at elevated temperatures to afford a trimeric Sm(III) cyanide (μ-C[triple bond, length as m-dash]N) complex. The isomeric isonitrile t-BuN[triple bond, length as m-dash]C undergoes the related reductive C–N bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(III) η2-iminoacyl (t-BuC[double bond, length as m-dash]N-t-Bu) complex.

Graphical abstract: Sm(ii) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitriles

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Supplementary files

Article information


Submitted
10 Feb 2010
Accepted
05 May 2010
First published
03 Jun 2010

Dalton Trans., 2010,39, 6864-6870
Article type
Paper

Sm(II) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitriles

M. G. Gardiner, A. N. James, C. Jones and C. Schulten, Dalton Trans., 2010, 39, 6864
DOI: 10.1039/C002778B

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