Ruthenaphosphaalkenyls: synthesis, structures, and their conversion to η2‑phosphaalkene complexes

Greenacre, Victoria K, Trathen, Nicola and Crossley, Ian R (2015) Ruthenaphosphaalkenyls: synthesis, structures, and their conversion to η2‑phosphaalkene complexes. Organometallics, 34 (11). pp. 2533-2542. ISSN 0276-7333

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Abstract

The ruthenaphosphaalkenyls [Ru{PCH-(SiMe2R)}Cl(CO)(PPh3)2] (R = Me, Ph, Tol) have been prepared in good yield by the facile hydroruthenation of the respective phosphaalkynes, RMe2SiCP, with [RuHCl(CO)-(PPh3)3]; all three compounds have been structurally characterized in the solid state. Complemented by DFT studies of these, and the precedent [Ru{PCH(tBu)}Cl(CO)(PPh3)2], the phosphaalkenyl moieties have been established unequivocally to behave as one-electron donors to the coordinately unsaturated, 15-electron “RuCl(CO)(PPh3)2” fragment, corroborating an earlier demonstration of nucleophilic character at phosphorus within the tert-butyl system. Notwithstanding, the ruthenaphosphaalkenyls are shown to react with the nucelophiles Lipz′ (pz′ = pz, pz*, pzH,CF3, pzMe,CF3) to afford the η1,η2-chelated pyrazolylphosphaalkene complexes [Ru{η1-N:η2-P,C-P(pz′)CH(R)}(CO)(PPh3)2], which feature a three-membered metallacyclic (Ru−C−P) core. The nature of these novel compounds is discussed, alongside preliminary insight into the process by which they are formed.

Item Type: Article
Keywords: organometallic, phosphacarbon, phosphaalkene
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Depositing User: Ian Crossley
Date Deposited: 06 May 2015 08:12
Last Modified: 07 Mar 2017 04:40
URI: http://sro.sussex.ac.uk/id/eprint/53878

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Project NameSussex Project NumberFunderFunder Ref
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wiresG1182ROYAL SOCIETYUF120021
The Development and Application of Organometallic Cyaphide Chemistry. University Research Fellowship (Fellow: Ian Crossley)G0136ROYAL SOCIETY516002.K501/SC
Crossley - Conjugate phosphapolyynyls: en route to functional phosphaorganometallic polymersG0200LEVERHULME TRUSTF/00 230/AL