[EN] COMPLEXES OF PHOSPHINE LIGANDS COMPRISING A CARBA-CLOSO-DODECABORATE SUBSTITUENT<br/>[FR] COMPLEXES DE LIGANDS DE PHOSPHINE COMPRENANT UN SUBSTITUANT CARBA-CLOSO-DODÉCARBORATE
申请人:UNIV CALIFORNIA
公开号:WO2014071401A1
公开(公告)日:2014-05-08
This invention relates to complexes comprising phosphine ligands comprising a carbo-closo-dodecaborate substituent and transition metals as well as their use in catalytic reactions.
Perhalogenated Carba-<i>closo</i>-dodecaborate Anions as Ligand Substituents: Applications in Gold Catalysis
作者:Vincent Lavallo、James H. Wright、Fook S. Tham、Sean Quinlivan
DOI:10.1002/anie.201209107
日期:2013.3.11
Bigger and better! The single‐component zwitterionic gold catalyst formed by the coordination of a phosphine ligand bearing an inert and noncoordinating carborane substituent, CB11Cl11−, to an AuI ion exhibited the highest reported activity for the hydroamination of alkynes with amines (see scheme). The highest turnover number observed for hydroamination with this catalyst exceeded a stunning 95 000
reveal that 3 exhibits a remarkably different structure in comparison with the reported Ge(I) radical C (L′•Ge:, L′ = [HC(tBuCN-Dip)2]−). The inductive effect of three phenyl groups leads to the backbone of ligand 1 being more electron deficient, and therefore the singly occupied molecular orbital (SOMO) of radical 3 is mainly composed of a π-antibonding orbital between the N and C atoms. This results in
使用在配体主链上具有三个苯基的新型β-二酮亚胺1a(PhCH(PhC═N-Dip)2,Dip = 2,6- i Pr 2 C 6 H 3),我们合成了β-二酮亚胺对二甲苯氯化物2(LGeCl,L = [PhC(PhCN-Dip)2 ] -)。β-二酮基锗原子自由基复合物3(• LGe :, • L = • [PhC(PhCN-Dip)2 ] 2–已通过用钠/萘还原LGeCl以64%的收率进行分离。X射线衍射,HR-MS,和电子顺磁共振分析连同DFT计算表明3周表现出显着不同的结构与文献报道的葛(I)基团的比较Ç(L' •葛:, L'= [HC(t BuCN-Dip)2 ] -)。三个苯基的感应作用导致配体1的主链更加缺乏电子,因此基团3的单个占据的分子轨道(SOMO)主要由N和C原子之间的π反键轨道组成。这导致约。N-Ge键短约0.14Å,约 与C中观察到的键相比,C–N键在3中长0.1Å