Vinyl and carbene ruthenium(<scp>ii</scp>) complexes from hydridoruthenium(<scp>ii</scp>) precursors
作者:Stefan Jung、Carsten D. Brandt、Justin Wolf、Helmut Werner
DOI:10.1039/b314425a
日期:——
hydrido compounds [RuHCl(CO)(L)2][L = PiPr3 (1), PCy3 (2)] with HC(triple bond)CR (R = H, Ph, tBu) afforded by insertion of the alkyne into the Ru-H bond the corresponding vinyl complexes [RuCl(CHCHR)(CO)(L)2], 3-8, which upon protonation with HBF4 gave the cationic five-coordinated ruthenium carbenes [RuCl(CHCH2R)(CO)(L)2]BF4, 9-14. Subsequent reactions of the carbene complexes with PR3(R = Me, iPr)
氢化物[RuHCl(CO)(L)2] [L = PiPr3(1),PCy3(2)]与HC(三键)CR(R = H,Ph,tBu)的反应是通过插入炔烃进入相应的乙烯基络合物[RuCl(CHCHR)(CO)(L)2,3-8)形成Ru-H键,在用HBF4质子化后得到阳离子五配位钌碳烯[RuCl(CHCH2R)(CO) (L)2] BF4,9-14。卡宾配合物与PR3(R = Me,iPr)和CH3CN的后续反应导致乙烯基化合物的去质子化和再生或钌-卡宾键的裂解和六配位配合物[RuCl( CO)(CH3CN)2(PiPr3)2] BF4,17和[RuH(CO)(CH3CN)2(PiPr3)2] X,18a,b。乙酰基衍生物[RuH(2-O2CCH3)(CO)(PCy3)2],19,也通过插入与乙炔和苯乙炔反应生成相关的乙烯基络合物[Ru(CHCHR)(kappa2-O2CCH3)(CO)(PCy3)2],20、21,其中R