Limits of delocalization in through-conjugated dinitrenes: Aromatization or bond formation?

被引：39

作者：

Serwinski, PR ^{[1
]}

Lahti, PM ^{[1
]}

机构：

[1] Univ Massachusetts, Dept Chem, Amherst, MA 01003 USA

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 12期

关键词：

D O I：

10.1021/ol034511c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Dinitrenes 4 and 5 both can form quinonoidal structures by conjugative bond formation. However, ESR spectroscopy detects a thermally populated, excited-state, triplet quinonoidal structure only for 4, with a zero-field splitting of \D/hc\ = 0.0822 cm(-1), \E/hc\ congruent to 0.0 cm(-1). The tendency to maintain aromaticity in the additional ring of 5 favors a dinitrene structure (with one less formal x-bond) over a quinonoidal structure. The thermally populated quintet state of 5 has a zero-field splitting of \D/hc\ = 0.287 cm(-1), \E/hc\ less than or equal to 0.002 cm(-1).

引用

页码：2099 / 2102

页数：4

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