Cr(i)Cl as well as Cr+ are stabilised between two cyclic alkyl amino carbenes

2015 | journal article. A publication with affiliation to the University of Göttingen.

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​Cr(i)Cl as well as Cr+ are stabilised between two cyclic alkyl amino carbenes​
Samuel, P. P.; Neufeld, R.; Chandra Mondal, K.; Roesky, H. W.; Herbst-Irmer, R.; Stalke, D. & Demeshko, S. et al.​ (2015) 
Chemical Science6(5) pp. 3148​-3153​.​ DOI: https://doi.org/10.1039/c5sc00646e 

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Authors
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.
Abstract
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)2CrCl2 (1) with equivalent amount of KC8 results in the formation of (cAAC)2CrCl (2), with a distorted trigonal planar configuration at the metal centre. SQUID, EPR and theoretical studies reveal a Cr(I) centre with S = 5/2 spin ground state for 2. It represents the first example of a mononuclear Cr complex showing slow relaxation of magnetisation under an applied magnetic field. The chlorine atom in 2 is expected to be prone to further reactions with appropriate reagents. This qualifies 2 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 2 is treated with Na[B(C6H3(CF3)2)4] resulting in [(cAAC)2Cr]+[B(C6H3(CF3)2)4]−, a linear cationic complex with two coordinate Cr(I) and an S = 5/2 spin ground state.
Issue Date
2015
Status
published
Publisher
Royal Soc Chemistry
Journal
Chemical Science 
Organization
Fakultät für Chemie 
ISSN
2041-6539; 2041-6520
Language
English

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