NEOPHYL-LIKE REARRANGEMENT OF ALKOXY RADICALS - DIRECT DETECTION OF A BRIDGED INTERMEDIATE BY TIME-RESOLVED ABSORPTION-SPECTROSCOPY

被引：44

作者：

FALVEY, DE ^{[1
]}

KHAMBATTA, BS ^{[1
]}

SCHUSTER, GB ^{[1
]}

机构：

[1] UNIV ILLINOIS,ROGER ADAMS LAB,DEPT CHEM,URBANA,IL 61801

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1990年 / 94卷 / 03期

关键词：

D O I：

10.1021/j100366a006

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The neophyl-like rearrangement of alkoxy radicals was examined by means of picosecond time scale absorption spectroscopy. The triphenylmethoxy radical (Ph3CO•) rearranges to form the α-phenoxydiphenylmethyl radical (Ph2COPh•) with a rate constant greater than 5 × 1010 s-1. The rearrangement of 1,1-diphenylethoxy radical (PhCH3CO•) was also examined. In acetonitrile solution, an intermediate is formed in less than 17 ps and then decays with a lifetime of 312 ns. It is proposed that this intermediate is a bridged spiro[2.6]octadiene-type radical. © 1990 American Chemical Society.

引用

页码：1056 / 1059

页数：4

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