Enolate-Phosphane Ligands Providing a Tool for the Selective Substitution of Triphenylphosphane by Carbon Monoxide or Trimethylphosphane in Complex {Ru(Cp)[η2-P,O-Ph2PCH2C(tBu)=O](PPh3)}[PF6], and Subsequent Reactivity Towards Terminal Alkynes
✍ Scribed by Bernard Demerseman; Loïc Toupet
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- English
- Weight
- 203 KB
- Volume
- 2006
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
The deprotonation under basic conditions of the keto‐phosphane ligand in complexes {Ru(Cp)η^1^‐P‐Ph~2~PCH~2~C(=O)__t__Bu(L)}[PF~6~] (L = CO or PMe~3~) that arise from the addition of L to {Ru(Cp)η^2^‐P,O‐Ph~2~PCH~2~C(__t__Bu)=O}[PF~6~] generates {Ru^+^(Cp)η^1^‐P‐Ph~2~PCH=C(__t__Bu)O^–^(L)} zwitterionic species, as shown by an X‐ray crystal structure determination (L = CO). The removal of the triphenylphosphane ligand is subsequently achieved under thermal activation to afford the neutral derivatives Ru(Cp)η^2^‐P,O‐Ph~2~PCH=C(__t__Bu)O. A further protonation step is sufficient to complete the formation of the new complex {Ru(Cp)η^2^‐P,O‐Ph~2~PCH~2~C(__t__Bu)=O}[PF~6~], which reacts in methanolat reflux with 1,1‐diphenyl‐2‐propyn‐1‐ol to afford thesix‐membered metallacyclic derivative {Ru(Cp)η^2^‐C,P:C(CH=CPh~2~)OC(__t__Bu)=CH–PPh~2~}[PF~6~], as shown by an X‐ray single crystal analysis. The synthesis of related η^5^‐indenyl ruthenium complexes and of {Ru(Cp)(=C=CH~2~)Ph~2~PCH~2~C(=O)__t__Bu}[PF~6~] (PR~3~ = PPh~3~ or PMe~3~) vinylidene complexes is also reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)