Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja4123285
Title: Stabilization of a Cobalt Cobalt Bond by Two Cyclic Alkyl Amino Carbenes
Authors: Mondal, Kartik Chandra
Samuel, Prinson P
Roesky, Herbert W
Carl, Elena
Herbst-Irmer, Regine
Stalke, Dietmar
Schwederski, Brigitte
Kaim, Wolfgang
Ungur, Liviu 
Chibotaru, Liviu F
Hermann, Markus
Frenking, Gernot
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
COMPLEXES
CYCLOPROPANATION
INTERMEDIATE
ACTIVATION
CHLORIDES
ADDUCTS
LIGAND
DIMER
ARYL
IRON
Issue Date: 5-Feb-2014
Publisher: AMER CHEMICAL SOC
Citation: Mondal, Kartik Chandra, Samuel, Prinson P, Roesky, Herbert W, Carl, Elena, Herbst-Irmer, Regine, Stalke, Dietmar, Schwederski, Brigitte, Kaim, Wolfgang, Ungur, Liviu, Chibotaru, Liviu F, Hermann, Markus, Frenking, Gernot (2014-02-05). Stabilization of a Cobalt Cobalt Bond by Two Cyclic Alkyl Amino Carbenes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136 (5) : 1770-1773. ScholarBank@NUS Repository. https://doi.org/10.1021/ja4123285
Abstract: (Me2-cAAC:)2Co2 (2, where Me 2-cAAC: = cyclic alkyl amino carbene,:C(CH2)(CMe 2)2N-2,6-iPr2C6H3)) was synthesized via the reduction of precursor (Me2-cAAC:Co II(μ-Cl)Cl)2 (1) with KC8. 2 contains two cobalt atoms in the formal oxidation state zero. Magnetic measurement revealed that 2 has a singlet spin ground state S = 0. The cyclic voltammogram of 2 exhibits both one-electron oxidation and reduction, indicating the possible synthesis of stable species containing 2•- and 2 •+ ions. The latter was synthesized via reduction of 1 with required equivalents of KC8 and characterized as [(Me 2-cAAC:)2Co2]•+OTf- (2•+OTf-). Electron paramagnetic resonance spectroscopy of 2•+ reveals the coupling of the electron spin with 2 equiv 59Co isotopes, leading to a (Co0.5) 2 state. The experimental Co1-Co2 bond distances are 2.6550(6) and 2.4610(6) Å for 2 and 2•+OTf-, respectively. Theoretical investigation revealed that both 2 and 2•+OTf - possess a Co-Co bond with an average value of 2.585 Å. A slight increase of the Co-Co bond length in 2 is more likely to be caused by the strong π-accepting property of cAAC. 2•+ is only 0.8 kcal/mol higher in energy than the energy minimum. The shortening of the Co-Co bond of 2•+ is caused by intermolecular interactions. © 2014 American Chemical Society.
Source Title: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
URI: https://scholarbank.nus.edu.sg/handle/10635/228694
ISSN: 0002-7863
1520-5126
DOI: 10.1021/ja4123285
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