Reaction of the RuTp(PR3)Cl fragment with alkynols: Formation of carbene, vinylidene, allenylidene, and carbyne complexes

The reaction of RuTp(COD)Cl (1) with PR3 (PR3 = PPh2iPr, PiPr3, PPh3) and propargylic alcohols HCtriple bond; length of mdashCCPh2OH, HCtriple bond; length of mdashCCFc2OH (Fc = ferrocenyl), and HCtriple bond; length of mdashCC(Ph)MeOH has been studied.In the case of PR3 = PPh2iPr, PiPr3 and HCtriple bond; length of mdashCCPh2OH, the 3-hydroxyvinylidene complexes RuTp(PPh2iPr)(double bond; length as m-dashCdouble bond; length as m-dashCHC(Ph)2OH)Cl (2a) and RuTp(PiPr3)(double bond; length as m-dashCdouble bond; length as m-dashCHC(Ph2)OH)Cl (2b) were isolated.With PR3 = PPh2iPr and HCtriple bond; length of mdashCCFc2OH as well as with PR3 = PPh3 and HCtriple bond; length of mdashCCPh2OH dehydration takes place affording the allenylidene complexes RuTp(PPh2iPr)(double bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashCFc2)Cl (3b) and RuTp(PPh3)(double bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashCPh2)Cl (3c).Similarly, with PPh2iPr and HCtriple bond; length of mdashCC(Ph)MeOH rapid elimination of water results in the formation of the vinylvinylidene complex RuTp(PPh2iPr)(double bond; length as m-dashCdouble bond; length as m-dashCHC(Ph)double bond; length as m-dashCH2)Cl (4).In contrast to the reactions of the RuTp(PR3)Cl fragment with propargylic alcohols, with HCtriple bond; length of mdashC(CH2)nOH (n = 2, 3, 4, 5) six-, and seven-membered cyclic oxycarbene complexes RuTp(PR3)(double bond; length as m-dashC4H6O)Cl (5), RuTp(PR3)(double bond; length as m-dashC5H8O)Cl (6), and RuTp(PR3)(double bond; length as m-dashC6H10O)Cl (7) are obtained. On the other hand, with 1-ethynylcyclohexanol the vinylvinylidene complex RuTp(PPh2iPr)(double bond; length as m-dashCdouble bond; length as m-dashCHC6H9)Cl (8) is formed. The reaction of the allenylidene complexes 3a–c with acid has been investigated. Addition of CF3COOH to a solution of 3a–c resulted in the reversible formation of the novel RuTp vinylcarbyne complexes [RuTp(PPh2iPr)(triple bond; length of mdashC–CHdouble bond; length as m-dashCPh2)Cl]+ (9a), [RuTp(PPh2iPr)(triple bond; length of mdashC–CHdouble bond; length as m-dashCFc2)Cl]+ (9b), and [RuTp(PPh3)(triple bond; length of mdashC–CHdouble bond; length as m-dashCPh2)Cl]+ (9c). The structures of 3a, 3b, and 5b have been determined by X-ray crystallography.