Carbon–oxygen bond cleavage in allylic esters promoted by low‐valent transition‐metal hydride complexes
Carbon–oxygen bond cleavage in allylic esters promoted by low‐valent transition‐metal hydride complexes
复制标题
低价过渡金属氢化物配合物促进烯丙酯中的碳-氧键断裂
DOI：
10.1002/aoc.590070803
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发表时间：
1993
影响因子：
3.9
通讯作者：
R. Srivastava
中科院分区：
文献类型：
--
作者：
R. Srivastava
CoH（N2）（PPh 3）3在室温下促进烯丙基羧酸酯中的碳-氧（CO）键断裂以得到相应的烯烃。另一方面，RuH 2（PPh 3）4和RhH（PPh 3）4在高温下主要对CO键断裂具有活性。反应通过一种机制进行，该机制涉及从RuH 2（PPh 3）4和RhH（PPh 3）4的叔膦之一的预解离和烯丙基羧酸和PPh 3到钌和铑上的空位的竞争性配位。合成了一个新的六元双环配合物Co（OCOCH_2COCH_3）（PPh_3）_2。
CoH(N2)(PPh3)3 promotes carbon–oxygen (CO) bond cleavage in allylic carboxylates to give the corresponding olefins at room temperature. On the other hand, RuH2(PPh3)4 and RhH(PPh3)4 are mainly active for CO bond cleavage at elevated temperature. Reaction proceeds through a mechanism involving predissociation of one of the tertiary phosphines from the RuH2(PPh3)4 and RhH(PPh3)4 and competitive coordination of allylic carboxylates and PPh3 to the vacant site on ruthenium and rhodium. A new six-membered metallocyclic complex, Co(OCOCH2COCH3)(PPh3)2, has been isolated.