Synthesis and Reactivity of an Aminocarbene Osmium Complex Formed by Double C–H Activation of a NCH
<sub>3</sub>
Unit
作者:Birgit Richter、Helmut Werner
DOI:10.1002/ejic.200900759
日期:2009.11
[OsCl 2 (PPh 3 ) 3 ] (1) with iPr 2 PCH 2 CH 2 NMe 2 in 2-propanol under reflux affords the Fischer-type aminocarbene complex cis,cis-[OsCl 2 κ 2 (C,P)-CHN(CH 3 )CH 2 CH 2 -PiPr 2 )κ 2 (aN)-iPr 2 PCH 2 CH 2 NMe 2 }] (2) by double C―H activation of one NCH 3 group. While treatment of 2 with phenylacetylene leads to the vinylidene complex cis,trans-[OsCl 2 (C=CHPh)κ 2 (C,P)-CHN(CH 3 )CH 2 CH 2 PiPr
[OsCl 2 (PPh 3 ) 3 ] (1) 与 iPr 2 PCH 2 CH 2 NMe 2 在 2-丙醇中回流反应得到 Fischer 型氨基卡宾配合物 cis,cis-[OsCl 2 κ 2 (C, P)-CHN(CH 3 )CH 2 CH 2 -PiPr 2 )κ 2 (aN)-iPr 2 PCH 2 CH 2 NMe 2 }] (2) 通过一个NCH 3 基团的双C-H活化。虽然用苯乙炔处理 2 会产生亚乙烯基络合物 cis,trans-[OsCl 2 (C=CHPh)κ 2 (C,P)-CHN(CH 3 )CH 2 CH 2 PiPr 2 }κ(P)- iPr 2 -PCH 2 CH 2 NMe 2 }] (3) 通过部分打开 P,N-螯合键,2 与 CO 和 CNtBu 的反应产生 [OsCl(L)(κ 2 ( C,P)-CHN(CH 3 )CH 2 CH 2 -PiPr