CHEMICAL MECHANISM OF DIOXYGEN ACTIVATION BY TRANS-[FECL2(CYCLAM)]+ (CYCLAM = 1,4,8,11-TETRAAZACYCLOTETRADECANE) IN THE PRESENCE OF REDUCING AGENTS SUCH AS ALIPHATIC-ALDEHYDES OR LINOLENIC ACID

被引：14

作者：

NISHIDA, Y

TANAKA, N

机构：

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1994年 / 19期

关键词：

D O I：

10.1039/dt9940002805

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex trans-[FeCl2(cyclam)]+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) was found to activate dioxygen in the presence of reducing agents such as an aliphatic aldehyde or linolenic acid (octadeca-9,12,15-trienoicacid), leading to degradation of tetraphenylcyclopentadienone. The activity of the corresponding cis isomer is almost negligible. The origin of the high activity of the trans compound is discussed in terms of the results of extended-Huckel molecular-orbital calculations performed for the assumed intermediate. It is concluded that the formation of hydrogen bonding between dioxygen and the ligand is very important for activation of dioxygen in this system.

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页码：2805 / 2808

页数：4

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