Crossley_10.1021_om5012177.pdf (686.47 kB)
Ruthenaphosphaalkenyls: synthesis, structures, and their conversion to ?2-phosphaalkene complexes
journal contribution
posted on 2023-06-08, 20:41 authored by Victoria K Greenacre, Nicola Trathen, Ian CrossleyIan CrossleyThe 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 ?1,?2-chelated pyrazolylphosphaalkene complexes [Ru{?1-N:?2-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.
Funding
Crossley - Conjugate phosphapolyynyls: en route to functional phosphaorganometallic polymers; G0200; LEVERHULME TRUST; F/00 230/AL
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wires; G1182; ROYAL SOCIETY; UF120021
The Development and Application of Organometallic Cyaphide Chemistry. University Research Fellowship (Fellow: Ian Crossley); G0136; ROYAL SOCIETY; 516002.K501/SC
History
Publication status
- Published
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- Accepted version
Journal
OrganometallicsISSN
0276-7333Publisher
American Chemical SocietyExternal DOI
Issue
11Volume
34Page range
2533-2542Department affiliated with
- Chemistry Publications
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- Yes
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- Yes
Legacy Posted Date
2015-05-06First Open Access (FOA) Date
2016-05-05First Compliant Deposit (FCD) Date
2015-05-05Usage metrics
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