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Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2018-02-05 , DOI: 10.1002/chem.201800147
Stefan Vanicek 1 , Maren Podewitz 1 , Christopher Hassenrück 2 , Michael Pittracher 1 , Holger Kopacka 1 , Klaus Wurst 1 , Thomas Müller 3 , Klaus R Liedl 1 , Rainer F Winter 2 , Benno Bildstein 1
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Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na2 Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different from common N-heterocyclic carbenes. Its ligand properties (TEP, singlet-triplet gap, nucleophilicity, π-acidity, Brønsted basicity) are in part comparable to those of cyclic (amino)(alkyl/aryl)carbenes. Electrochemistry data showed that the mesoionic cobaltoceniumides are more electron-rich than their parent ferrocenes. The reversible reduction of the tricyanido gold complex appears 50 mV negative of the cobaltocenium/cobaltocene couple, whereas that of the selenide derivative is shifted cathodically by 550 mV.

中文翻译:

Cobaltocenylidene:中离子茂金属卡宾,稳定在金 (III) 络合物中。

用(伪)卤化物金酸盐氧化加合铕重氮鎓双(六氟磷酸盐)得到含有两性离子铕鎓作为配体的金(III)配合物。其硒衍生物Cobaltoceniumselenolate是通过碘化钴与Na2Se的亲电芳香取代反应获得的。光谱和结构数据结合 DFT 计算表明,这种二亚钴胺是一种与常见的 N-杂环卡宾完全不同的介离子卡宾。其配体特性(TEP、单线态-三线态间隙、亲核性、π-酸度、布朗斯台德碱度)部分与环状(氨基)(烷基/芳基)卡宾相当。电化学数据表明,介离子茂钴化物比其母体二茂铁更富电子。
更新日期:2018-02-05
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