PHOTOPROTONATION OF A METAL NITRIDE COMPLEX

被引：13

作者：

VINING, WJ

NEYHART, GA

NIELSEN, S

SULLIVAN, BP

机构：

[1] UNIV WYOMING, DEPT CHEM, LARAMIE, WY 82071 USA

[2] HARTWICK COLL, DEPT CHEM, ONEONTA, NY 13820 USA

来源：

INORGANIC CHEMISTRY | 1993年 / 32卷 / 20期

关键词：

D O I：

10.1021/ic00072a011

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Protonation of both the ground and the excited states of trans-NRe(R2PCH2CH2PR2)2Cl+ has been shown to occur in HCI solution (R = Me). The product is the imido complex trans-HNRe(R2PCH2CH2PR2)2Cl2+. Titration of the ground and excited states yields apparent pK values of ca. -1.0 and 4.5, respectively, demonstrating a profound increase in bascisity in the excited state. This change, which can be rationalized by a simple orbital diagram, is due to an increase in electron density at the nitride nitrogen in the excited state. The related complex trans-NRe(CN)4(H2O)2- exhibits an apparent excited-state pK value of 3.6, indicating that 'tuning'' of the excited-state properties is possible by large changes in coordination sphere composition.

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页码：4214 / 4217

页数：4

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