Mapping the Elimination of Water from Hydroxyvinylidene Complexes of Ruthenium(II): Access to Allenylidene and Vinylvinylidene Complexes in a Stepwise Fashion
作者:Elizabeth J. Smith、David G. Johnson、Robert J. Thatcher、Adrian C. Whitwood、Jason M. Lynam
DOI:10.1021/om4009247
日期:2013.12.23
substituent present. In the case in which R1 = R2 = Ph, the hydrogen on the β-carbon of the organic ligand is removed to afford an allenylidenecomplex [Ru(κ1-OAc)(κ2-OAc)(═C═C═CPh2)(PPh3)2]. An examination of the structural and spectroscopic parameters for the allenylidenecomplex indicates that the electronic influence of this ligand is very similar to the corresponding vinylidene and isonitrile analogues
hydroxyvinylidene络合物的反应的[Ru(κ 1 -OAc)(κ 2 -OAc)(═C═CHCOH} - [R 1 - [R 2)(PPH 3)2 ](R 1 = R 2 =苯基; R 1 = R 2 =我; R 1 =苯基,R 2 = Me)的用[器CPh 3 ] BF 4个导致形成阳离子卡宾物种[茹(κ 2 -OAc)(OC 我}ö CC H} = CR 1 R 2)(PPh 3)2 ] BF 4。在这些配合物,κ 1-乙酸酯配体改变了其结合模式,以稳定所得的阳离子物质。卡宾配合物可以被去质子化,尽管反应的结果明显取决于存在的取代基。在这种情况下,其中R 1 = R 2 =苯基,对有机配体的β碳上的氢被除去,得到复合物的allenylidene的[Ru(κ 1 -OAc)(κ 2 -OAc)(═C═C ═CPh 2)(PPH 3)2 ]。对亚烯基络合物的结构和光谱参