Reactions of Alkynyl−Ruthenium Complexes with the Ketene Dithioacetal, (MeS)₂CC(CN)₂

Reactions of several alkynyl−ruthenium complexes with the ketene dithioacetal (MeS)2CC(CN)2 (2) are described. The first examples of metalated 6-alkylthio-6-azafulvenes, Ru{CCRC(SMe)C(CN)CN(SMe)}(PPh3)Cp [R = Ph (5a), Fc (5b)], were obtained from Ru(CCR)(PPh3)2Cp, while Ru(CCPh)(CO)(PPh3)Cp gave dienyl complexes Ru{C(SMe)CPhC(SMe)C(CN)2}(CO)(PPh3)nCp [n = 1 (8), 0 (9)]. Yields of the azafulvenes were increased under conditions conducive to radical formation. The reaction between 5 and Ru(CCCCPh)(PPh3)2Cp afforded the alkynyl−dienyl Ru{C(SMe)C(CCPh)C(SMe)C(CN)2}(PPh3)Cp (11) and the dienynyl Ru{CCC(SMe)CPhC(SMe)C(CN)2}(PPh3)2Cp (12), formed by formal insertion of either CC triple bond into one C−S bond. The reaction of Ru(CCPh)(PPh3)2Cp with dimethyl 2,3-dicyanofumarate (3) afforded diastereomers of the η3-dienyl complex Ru{η3-C(CN)(CO2Me)CPhCC(CN)(CO2Me)}(PPh3)Cp (13). XRD structural determinations of 5a, 8, 9, 11, and one diastereomer of 13 are reported.本文报道了数种炔基钌配合物与烯酮二硫缩醛（ketene dithioacetal）(MeS)₂C=C(CN)₂（化合物2）的反应。首次得到了金属化6-烷基硫代-6-氮杂富烯（6-alkylthio-6-azafulvenes）类化合物Ru{C=CRC(SMe)=C(CN)C=N(SMe)}(PPh₃)Cp，其中PPh₃为三苯基膦（triphenylphosphine, PPh₃）、Cp为环戊二烯基（cyclopentadienyl, Cp），R为苯基（phenyl, Ph, 5a）、二茂铁基（ferrocenyl, Fc, 5b），该类产物由Ru(C≡CR)(PPh₃)₂Cp反应制得；而Ru(C≡CPh)(CO)(PPh₃)Cp则生成了二烯基（dienyl）配合物Ru{C(SMe)=CPhC(SMe)=C(CN)₂}(CO)(PPh₃)ₙCp [n=1（8）、0（9）]。在利于自由基生成的反应条件下，该类氮杂富烯类产物的收率得以提升。化合物5与Ru(C≡CC≡CPh)(PPh₃)₂Cp的反应生成了炔基二烯基配合物Ru{C(SMe)=C(C≡CPh)C(SMe)=C(CN)₂}(PPh₃)Cp（11）与烯二炔基配合物Ru{C≡CC(SMe)=CPhC(SMe)=C(CN)₂}(PPh₃)₂Cp（12），二者均为通过将其中一条C≡C三键形式插入至一条C-S键中而生成。Ru(C≡CPh)(PPh₃)₂Cp与2,3-二氰基富马酸二甲酯（化合物3）的反应生成了η³-二烯基（η³-dienyl）配合物Ru{η³-C(CN)(CO₂Me)CPhC=C(CN)(CO₂Me)}(PPh₃)Cp（13）的多种非对映异构体。本文还对化合物5a、8、9、11以及13的其中一种非对映异构体进行了X射线衍射（X-ray Diffraction, XRD）结构表征。