Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes
作者:Andrew J. Roering、Sarah E. Leshinski、Stephanie M. Chan、Tamila Shalumova、Samantha N. MacMillan、Joseph M. Tanski、Rory Waterman
DOI:10.1021/om100216f
日期:2010.6.14
(N3N = N(CH2CH2NSiMe3)33−; R = alkyl, aryl; R′ = R, H), have been shown to catalyze the hydrophosphination of terminal alkynes as well as that of symmetric aryl and alkyl carbodiimides. A mechanism based on insertion of the substrate into the Zr−P bond is proposed on the basis of competition experiments and model examples of stoichiometric insertion reactions of polar, small-molecule substrates possessing
Triamidoamine支持锆膦配合物,(N 3 N)ZrPRR'(N 3 N = N(CH 2 CH 2 NSiMe 3)3 3- ; R =烷基,芳基; R'= R,H),已经显示出催化末端炔烃以及对称的芳基和烷基碳二亚胺的氢磷化。在竞争实验和具有C proposedO,C═N,C≡N和C的极性小分子底物的化学计量插入反应的模型实例的基础上,提出了基于将底物插入Zr-P键的机理。 C═S功能进入Zr-P键。插入产物(N 3 N)ZrN═C(PHCy)Ph(4),(N 3的分子结构N)ZrN═C(PPH 2)PH(5),和(N 3 N)ZrPhNC(O)PPH 2(11),以及(N 3 N)的Zr [η 2(N,N-) - (我PrN)2 C(PPh 2)](9)是碳二亚胺催化加氢磷酸化的关键中间体,现已确定。