Characterization and reactions of previously elusive 17-electron cations:: Electrochemical oxidations of (C6H6)Cr(CO)3 and (C5H5)Co(CO)2 in the presence of [B(C6F5)4]-

被引：67

作者：

Camire, N ^{[1
]}

Nafady, A ^{[1
]}

Geiger, WE ^{[1
]}

机构：

[1] Univ Vermont, Dept Chem, Burlington, VT 05405 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 25期

关键词：

D O I：

10.1021/ja012641f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The electrochemical oxidations of (C6H6)Cr(CO)3, 1, and (C5H5)Co(CO)2, 2, when carried out in CH2Cl2/[NBu4][B(C6F5)4], allow the physical or chemical characterization of the 17-electron cations 1+ and 2+ at room temperature. The generation of 1+ on a synthetic time scale permits an electrochemical "switch" process involving facile substitution of CO by PPh3 as a route to (C6H6)Cr(CO)2PPh3. The radical 2+ undergoes a second-order reaction to give a product assigned as the metal-metal bonded dimer dication [Cp2Co2(CO)4]2+. The new anodic chemistry of these often-studied 18-electron compounds is made possible by increases in the solubility and thermal stability of the cation radicals in media containing the poorly nucleophilic anion [B(C6F5)4]-, TFAB. Copyright © 2002 American Chemical Society.

引用

页码：7260 / 7261

页数：2

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[32] ELECTRONIC-STRUCTURE AND BONDING CHARACTERISTICS OF CYCLOPENTADIENYL-D8 METAL-LIGAND COMPLEXES - CORE AND VALENCE IONIZATION STUDY OF CPM(CO)2 WHERE M = CO AND RH AND CP = ETA-5-C5H5 AND ETA-5-C5(CH3)5 [J].