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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

Citation

Gardiner, MG and James, AN and Jones, C and Schulten, C, 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, Dalton Transactions, 39, (29) pp. 6864-6870. ISSN 1477-9226 (2010) [Refereed Article]

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Copyright Statement

Copyright 2010 The Royal Society of Chemistry

Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/2010...

DOI: doi:10.1039/c002778b

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每P reductively coupled complex of (t-BuCPPC-t-Bu)2− featuring a new 米-灰2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(II) adducts that undergo reductive C每C bond cleavage at elevated temperatures to afford a trimeric Sm(III) cyanide (米-CN−) complex. The isomeric isonitrile t-BuNC undergoes the related reductive C每N bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(III) 灰2-iminoacyl (t-BuCN-t-Bu)− complex.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:f-Block Chemistry
Objective Division:Manufacturing
Objective Group:Industrial Chemicals and Related Products
Objective Field:Inorganic Industrial Chemicals
Author:Gardiner, MG (Associate Professor Michael Gardiner)
Author:James, AN (Mr Adam James)
ID Code:64662
Year Published:2010
Web of Science® Times Cited:13
Deposited By:Chemistry
Deposited On:2010-08-16
Last Modified:2011-05-11
Downloads:0

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