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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¡ä-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¨CP reductively coupled complex of (t-BuCPPC-t-Bu)2− featuring a new ¦Ì-¦Ç2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(II) adducts that undergo reductive C¨CC bond cleavage at elevated temperatures to afford a trimeric Sm(III) cyanide (¦Ì-CN−) complex. The isomeric isonitrile t-BuNC undergoes the related reductive C¨CN bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(III) ¦Ç2-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 |
| UTAS Author: | Gardiner, MG (Associate Professor Michael Gardiner) |
| UTAS Author: | James, AN (Mr Adam James) |
| ID Code: | 64662 |
| Year Published: | 2010 |
| Web of Science® Times Cited: | 14 |
| Deposited By: | Chemistry |
| Deposited On: | 2010-08-16 |
| Last Modified: | 2011-05-11 |
| Downloads: | 0 |
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