On the Synthesis and Reduction of Trigonal Halido Bis(silylamido) Metalates of Chromium to Cobalt
作者:Ruth Weller、Lena Völlinger、C. Gunnar Werncke
DOI:10.1002/ejic.202100716
日期:2021.11.15
The general synthesis of trigonal bromido metal(II) silylamides via adduct formation with tetrabutylammonium bromide or oxidation of linear metal(I) complexes as well as their reduction is presented. The adduct formation is also extended to benzyl potassium yielding benzyl manganese and cobalt complexes.
介绍了通过与四丁基溴化铵形成加合物或线性金属 (I) 配合物的氧化以及它们的还原来合成三方溴化金属 (II) 甲硅烷基酰胺。加合物的形成也扩展到苄基钾,产生苄基锰和钴配合物。
C−H Bond Activation by an Imido Cobalt(III) and the Resulting Amido Cobalt(II) Complex
作者:Alexander Reckziegel、Clemens Pietzonka、Florian Kraus、C. Gunnar Werncke
DOI:10.1002/anie.201914718
日期:2020.5.25
the isolation and characterisation of a rare, trigonal imido cobalt(III) complex, which bears a rather long cobalt-imido bond. It can cleanly cleave strong C-H bonds with a bond dissociation energy of up to 92 kcal mol-1 in an intermolecular fashion, unprecedented for imido cobaltcomplexes. This resulted in the amido cobalt(II) complex [Co(hmds)2 (NHt Bu)]- . Kinetic studies on this reaction revealed
3d-金属介导的氮宾转移由于其作为一种原子经济和生态良性方式用于(未)功能化CH键的定向胺化的潜力而受到严格审查。在这里,我们介绍了一种罕见的三角亚氨基钴(III)络合物的分离和表征,该络合物具有相当长的钴亚氨基键。它可以以高达 92 kcal mol-1 的键解离能以分子间方式干净地裂解强 CH 键,这对于亚氨基钴配合物来说是前所未有的。这产生了酰胺基钴(II)络合物[Co(hmds)2 (NHt Bu)]-。该反应的动力学研究揭示了氢原子转移机制。值得注意的是,酰胺钴 (II) 本身能够介导 H 原子夺取或逐步质子/电子转移,具体取决于底物。提出了使用有机叠氮化物进行钴介导的底物脱氢催化应用。
Cobalt PNC<sup>NHC</sup> ‘pincers’: ligand dearomatisation, formation of dinuclear and N<sub>2</sub> complexes and promotion of C–H activation
作者:Thomas Simler、Pierre Braunstein、Andreas A. Danopoulos
DOI:10.1039/c5cc10121b
日期:——
Studies of ligand dearomatisation in cobalt phosphino-picoline N-heterocyclic carbene (PNCNHC)-type pincers have revealed the formation of dinuclearcobaltcomplexes by either side-arm metalation or C-H activation at the NHC backbone;...
[EN] ALKOXIDE COMPOUND, THIN FILM-FORMING MATERIAL, AND METHOD FOR MANUFACTURING THIN FILM<br/>[FR] COMPOSÉ ALCOXYDE, MATÉRIAU DE FORMATION DE COUCHE MINCE ET PROCÉDÉ DE FABRICATION DE COUCHE MINCE<br/>[JA] アルコキシド化合物、薄膜形成用原料及び薄膜の製造方法
NHC‐Stabilized Parent Phosphinidene Adducts of Metal(II) Hexamethyldisilazanides of Manganese – Cobalt and Their Lability in Solution
作者:Ruth Weller、Andres Gonzalez、Hannah Gottschling、Carsten von Hänisch、C. Gunnar Werncke
DOI:10.1002/zaac.202100338
日期:2022.9.13
all compounds exhibit strong paramagnetism that limited NMR spectroscopic examinations to cobalt. Here it shows that the system is coordinatively highly fluxional, which is mitigtated upon cooling. At low temperatures, small amounts of free phosphinidene becomes further evident by 31P NMR spectroscopy that implicates in part ligand coordination competes with [MN(SiMe3)2}2] dimerisation and an overall