CATALYTIC C-C BOND FORMATION VIA ORTHO-METALATED COMPLEXES
CATALYTIC C-C BOND FORMATION VIA ORTHO-METALATED COMPLEXES
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DOI：
10.1021/ja00270a036
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发表时间：
1986-05-14
影响因子：
15
通讯作者：
SMITH, JF
中科院分区：
文献类型：
--
作者：
LEWIS, LN;SMITH, JF
邻金属化钌配合物I和II与乙烯反应生成邻乙基化亚磷酸产物。配合物II反应生成含有5和6个乙基/磷的产物P (0 (2,6 - et2 - c6h3)) 2 (0 (2- et - c6h4))（III5）和P (0 (2,6 - et3 - c6h3))) 3 (III6)，而配合物I主要反应生成亚硝酸盐产物P (0 (2,6 - et2 - c6h3)) 2 (OPh)（III4）和P (0 (2,6 - et2 - c6h3)) 2 (0 (2- et - c6h4))（III5）。配合物II和KOPh是苯酚与乙烯选择性邻乙基化的助催化剂。与乙烯反应相比，I与丙烯反应得到的烷基化程度较低，即P (0 (2,6 -(/- pr) 2- c6h3))(OPh) 2 （IV2）。苯乙烯与I反应的产物是含有磷酸三苯基的低分子量聚苯乙烯。插入反应的机制包括乙烯取代亚磷酸酯，乙烯插入（形成CC键）到Ru-C键，邻位金属化，最后还原消除得到乙基。该反应的中间体是由acacRh (C2H4) 2 (X)，“膦”生成的
The ortho-metalated ruthenium complexes I and II react with ethyleneto give ortho-ethylated phosphite products.Complex II reacts to give products with fiveand six ethyl groups/phosphorus P (0 (2, 6-Et2-C6H3)) 2 (0 (2-Et-C6H4))(III5) and P (0 (2, 6-Et3-C6H3)) 3 (III6), while complex I reactsto mainly give the phosphite products P (0 (2, 6-Et2-C6H3)) 2 (OPh)(III4) and P (0 (2, 6-Et2-C6H3)) 2 (0 (2-Et-C6H4))(III5). Complex II and KOPh are cocatalysts for theselective ortho ethylationof phenol with ethylene. The reaction of I with propylene results in a lower degree of alkylation, ie, P (0 (2, 6-(/-Pr) 2-C6H3))(OPh) 2 (IV2), than is obtained from ethylene. The product of the reaction of styrene with I gives lowmolecular weight polystyrene containing a triphenyl phosphiteend group. A proposed mechanism for the insertion reaction involves phosphite substitution by ethylene, insertion (CC bond formation) of ethylene into the Ru-C bond, ortho-metalation, and finally reductive elimination to give an ethyl group. The proposed intermediates of the reaction are generated by use of acacRh (C2H4) 2 (X),“phosphine