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Unsymmetrical alkyne binding to a triruthenium centre : oxidative-addition of diphenyl ditelluride to the furyne cluster [Ru3(CO)7(μ-H)(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-dppm)]
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Ghosh, Shishir, Hogarth, Graeme, Kabir, Shariff E., Nordlander, Ebbe, Salassa, Luca and Tocher, Derek A.. (2011) Unsymmetrical alkyne binding to a triruthenium centre : oxidative-addition of diphenyl ditelluride to the furyne cluster [Ru3(CO)7(μ-H)(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-dppm)]. Journal of Organometallic Chemistry, Vol.696 (No.10). pp. 1982-1989. ISSN 0022-328X
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Official URL: http://dx.doi.org/10.1016/j.jorganchem.2010.10.045
Abstract
Oxidative-addition of PhTe(2)Ph to the furyne cluster [Ru(3)(CO)(7)(mu-H)(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru(3)(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru(3)(CO)(5)(mu-eta(2)-C(4)H(3)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru(3)(CO)(5)(mu-H)(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (7) and [Ru(3)(CO)(4)(mu-H){P(C(4)H(3)O)(3)}(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. (C) 2010 Elsevier B.V. All rights reserved.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Faculty of Science > Chemistry |
| Journal or Publication Title: | Journal of Organometallic Chemistry |
| Publisher: | Elsevier S.A. |
| ISSN: | 0022-328X |
| Date: | 15 May 2011 |
| Volume: | Vol.696 |
| Number: | No.10 |
| Page Range: | pp. 1982-1989 |
| Identification Number: | 10.1016/j.jorganchem.2010.10.045 |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Restricted or Subscription Access |
| Funder: | Ministry of Science and Information & Communication Technology, Government of the People's Republic of Bangladesh, Swedish International Development Agency (SIDA) , Swedish Research Council (VR) |
| URI: | http://wrap.warwick.ac.uk/id/eprint/41770 |
Data sourced from Thomson Reuters' Web of Knowledge
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