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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 isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b

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Title: 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 isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b
Authors: Gardiner, Michael G.1, James, Adam N.1, Jones, Cameron1, Schulten, Christian1
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. Jul2010, Vol. 39 Issue 29, p6864-6870. 7p.
Subjects: Chemical reduction, Alkynes, Scission (Chemistry), Nitriles, Isocyanides, Reactivity (Chemistry), Stereoisomers, Metal complexes
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-BuCP gives a dinuclear Sm(iii) P–P reductively coupled complex of (t-BuCPPC-t-Bu)2−featuring a new μ-η2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(ii) adducts that undergo reductive C–C bond cleavage at elevated temperatures to afford a trimeric Sm(iii) cyanide (μ-CN−) complex. The isomeric isonitrile t-BuNC 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-BuCN-t-Bu)−complex. [ABSTRACT FROM AUTHOR]
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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-BuCP gives a dinuclear Sm(iii) P–P reductively coupled complex of (t-BuCPPC-t-Bu)2−featuring a new μ-η2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(ii) adducts that undergo reductive C–C bond cleavage at elevated temperatures to afford a trimeric Sm(iii) cyanide (μ-CN−) complex. The isomeric isonitrile t-BuNC 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-BuCN-t-Bu)−complex. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/c002778b