Acceptor pincer Ru(ii) chemistry

Abstract

A series of new acceptor pincer Ru(II) complexes are reported. The carbonyl complex (^CF₃PCP)Ru(CO)Cl₂⁻Et₃NH⁺ is obtained from the reaction of ^CF₃PCPH with [(cod)Ru(μ-Cl)₂]_n. Chloride displacement with ^CF₃PCPH, CO, PPh₃, or C₂H₄ gave complexes of the type (^CF₃PCP)Ru(CO)(L)Cl, or in the case of ^CF₃PCPH, the bridged dimeric complex [(^CF₃PCP)Ru(CO)Cl]₂(μ-^CF₃PCPH). Chloride abstraction from (^CF₃PCP)Ru(CO)(L)Cl, L = CO or PPh₃ by (Et₃Si)₂(μ-H)⁺B(C₆F₅)₄⁻ followed by Et₃N addition produced (^CF₃PCP)Ru(CO)(L)(H) products. Reaction of cis-(^CF₃PCP)Ru(CO)₂Cl with (Et₃Si)₂(μ-H)⁺B(C₆F₅)₄⁻ in the presence of excess CO afforded (^CF₃PCP)Ru(CO)₃⁺. The reaction of ^CF₃PCPH with (PPh₃)₃Ru(H)(O₂CR) (R = Me or Ph) produced the corresponding carboxylate complexes (^CF₃PCP)Ru(PPh₃)(O₂CR).