Half-Sandwicho-N,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides
作者:Wen-Xiong Zhang、Masayoshi Nishiura、Tomohiro Mashiko、Zhaomin Hou
DOI:10.1002/chem.200701300
日期:2008.2.27
(7). The reaction of 6 or 7 with Ph2PH in THF yielded 4 and the phosphaguanidine iPrN=C(PPh2)NHiPr (3a). These results suggest that the catalytic formation of a phosphaguanidine compound proceeds through the nucleophilic addition of a phosphide species, which is formed by the acid-base reaction between a rare-earth metal o-dimethylaminobenzyl bond and a phosphine P--H bond, to a carbodiimide, followed
这些半三明治稀土金属氨基苄基络合物可作为有效的催化剂前体,用于催化将各种膦MH键与碳二亚胺催化加成,形成一系列对芳族碳-卤素键具有优异耐受性的磷胍衍生物。观察到催化活性的显着增加,这是由于金属尺寸的增加,总体趋势为La> Pr,Nd> Sm> Gd> Lu> Sc。2-La与1当量的Ph2PH反应生成相应的磷化物络合物[Me2Si(C5Me4)(NC6H2Me3-2,4,6)} La(PPh2)(thf)2](4),从苯,得到二聚体类似物[Me2Si(C5Me4)(NC6H2Me3-2,4,6)} La(PPh2)] 2(5)。在THF中将4或5加至iPrN = C = NiPr,得到磷胍盐配合物[Me2Si(C5Me4)(NC6H2Me3-2,4,6)} La iPrNC(PPh2)NiPr}(thf)](6),其在醚上重结晶后,得到醚配位的结构可表征的类似物[Me2Si(C5Me4)(NC6H2Me3-2