REACTIONS OF C-H BONDS IN ORGANIC OXYGENATES WITH OCTAETHYLPORPHYRINATO RHODIUM(II) AND IRIDIUM(II) DIMERS

被引：34

作者：

DELROSSI, KJ ^{[1
]}

ZHANG, XX ^{[1
]}

WAYLAND, BB ^{[1
]}

机构：

[1] UNIV PENN,DEPT CHEM,PHILADELPHIA,PA 19104

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1995年 / 504卷 / 1-2期

关键词：

RHODIUM; IRIDIUM; C-H ACTIVATION; METALLOPORPHYRINS;

D O I：

10.1016/0022-328X(95)05569-B

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Metalloporphyrin dimers, [(OEP)M](2) (la, M = Rh; Ib, M = Ir; OEP = octaethylporphyrin dianion), are observed to react with C-H bond units in aldehydes, ketones and benzyl alcohols. Aldehydes, R(2)CHCHO, preferentially react at the alkyl group adjacent to the carbonyl position to yield beta-formyl complexes, (OEP)M-CR(2)CHO, even when reaction of the aldehydic C-H unit is thermodynamically favored. Reaction at the carbon-hydrogen bond adjacent to the carbonyl group is proposed to occur by addition of the metalloporphyrin to the enol isomer to produce an intermediate alkyl bridged complex, (OEP)M-CR(2)CR'(OH)-M(OEP), which subsequently reacts by an effective beta-O-H migration to form (OEP)M-CR(2)C(O)R' and (OEP)M-H complexes. [(OEP)Rh](2) (la) also reacts with benzyl alcohols, C6H5CH(OH)R (R = H, CH3, C(O)C6H5), to produce intermediate alpha-hydroxyalkyl derivatives, (OEP)Rh-CR(OH)C6H5, which subsequently dissociate to give organic carbonyl species, C6H5C(O)R, and (OEP)Rh-H.

引用

页码：47 / 56

页数：10

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