Samuel Prinson P, Neufeld Roman, Chandra Mondal Kartik, Roesky Herbert W, Herbst-Irmer Regine, Stalke Dietmar, Demeshko Serhiy, Meyer Franc, Rojisha Vallyanga Chalil, De Susmita, Parameswaran Pattiyil, Stückl A Claudia, Kaim Wolfgang, Christian Jonathan H, Bindra Jasleen K, Dalal Naresh S
Institut für Anorganische Chemie , Georg-August-Universität , Tammannstrasse 4 , D-37077 , Göttingen , Germany . Email:
Department of Chemistry , National Institute of Technology Calicut , 673601 , Kerala , India . Email:
Chem Sci. 2015 May 1;6(5):3148-3153. doi: 10.1039/c5sc00646e. Epub 2015 Mar 20.
Cr(i)Cl is a very unstable species. The present work describes the stabilisation of Cr(i)Cl in the low coordinate environment of cyclic alkyl(amino) carbene ligands and its synthetic application to yield an unprecedented cationic complex with a two coordinate Cr(i). One electron reduction of (cAAC)CrCl () with equivalent amount of KC results in the formation of (cAAC)CrCl (), with a distorted trigonal planar configuration at the metal centre. SQUID, EPR and theoretical studies reveal a Cr(i) centre with = 5/2 spin ground state for . It represents the first example of a mononuclear Cr complex showing slow relaxation of magnetisation under an applied magnetic field. The chlorine atom in is expected to be prone to further reactions with appropriate reagents. This qualifies as a promising precursor for the preparation of various interesting complexes with Cr(i) in a low coordinate environment. The first example of this metathesis reaction is observed when is treated with Na[B(CH(CF))] resulting in [(cAAC)Cr][B(CH(CF))], a linear cationic complex with two coordinate Cr(i) and an = 5/2 spin ground state.
一氯化铬（Cr(i)Cl）是一种非常不稳定的物质。目前的工作描述了在环状烷基（氨基）卡宾配体的低配位环境中Cr(i)Cl的稳定化及其合成应用，以产生一种前所未有的具有二配位Cr(i)的阳离子配合物。用等量的KC对（cAAC）CrCl（）进行单电子还原，导致形成（cAAC）CrCl（），其金属中心具有扭曲的三角平面构型。超导量子干涉仪（SQUID）、电子顺磁共振（EPR）和理论研究表明，对于 ，Cr(i)中心具有5/2的自旋基态。它代表了单核Cr配合物在施加磁场下显示出磁化缓慢弛豫的第一个例子。预计 中的氯原子易于与适当的试剂发生进一步反应。这使 有资格成为在低配位环境中制备各种有趣的Cr(i)配合物的有前途的前体。当 用Na[B(CH(CF))]处理时，观察到这种复分解反应的第一个例子，得到[(cAAC)Cr][B(CH(CF))]，一种具有二配位Cr(i)和5/2自旋基态的线性阳离子配合物。
