Please use this identifier to cite or link to this item: https://doi.org/10.1002/ejic.201301598
Title: A Catalyst with Two-Coordinate Nickel: Theoretical and Catalytic Studies
Authors: Mondal, Kartik Chandra
Samuel, Prinson P
Li, Yan
Roesky, Herbert W
Roy, Sudipta
Ackermann, Lutz
Sidhu, Navdeep S
Sheldrick, George M
Carl, Elena
Demeshko, Serhiy
De, Susmita
Parameswaran, Pattiyil
Ungur, Liviu 
Chibotaru, Liviu F
Andrada, Diego M
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
NATURAL RESONANCE THEORY
DIRADICAL CHARACTER
ULLMANN SYNTHESIS
BOND ACTIVATION
COMPLEXES
LIGANDS
CARBENES
BULKY
Issue Date: 1-Feb-2014
Publisher: WILEY-V C H VERLAG GMBH
Citation: Mondal, Kartik Chandra, Samuel, Prinson P, Li, Yan, Roesky, Herbert W, Roy, Sudipta, Ackermann, Lutz, Sidhu, Navdeep S, Sheldrick, George M, Carl, Elena, Demeshko, Serhiy, De, Susmita, Parameswaran, Pattiyil, Ungur, Liviu, Chibotaru, Liviu F, Andrada, Diego M (2014-02-01). A Catalyst with Two-Coordinate Nickel: Theoretical and Catalytic Studies. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY 2014 (5) : 818-823. ScholarBank@NUS Repository. https://doi.org/10.1002/ejic.201301598
Abstract: The bisadduct (cAAC)2NiIICl2 [1; cAAC = cyclic (alkyl)(amino)carbene] was directly synthesized by treating cAAC with NiCl2. Compound 1 was reduced to (cAAC)2Ni (2) by using lithium diisopropylamide or KC8. Crystals of 2 were stable under an inert gas for several months and decomposed upon heating above 165°C. On the basis of the calculated natural bond orbital charge values of the nickel atom in 2, the oxidation state of nickel was determined to be between NiI and Ni (+0.34). Theoretical calculations suggested a closed-shell singlet electronic configuration of 2 with little biradical character. Ab initio multiconfigurational C(R)ASSCF/CASPT2 calculations predicted a closed-shell singlet electronic configuration (Ni), whereas excited spin states possessed NiI character with unpaired electrons on neighboring carbon atoms. The catalytic activity of complex 2 was investigated for the homocoupling of various unactivated aryl chlorides/fluorides. The biaryls were obtained in good yields at moderate temperature. Theoretical studies showed that an intermediate containing NiIII was more favored than one with NiIV. The synthesis of (cAAC)2NiIICl2 (1) and its conversion into (cAAC)2Ni (2) through reduction is reported [cAAC = cyclic (alkyl)(amino)carbene]. Efficient reductive homocoupling of unactivated aryl chlorides and fluorides is catalyzed by 2 through C-Cl and C-F bond activation. Detailed high-level theoretical investigations are performed to understand the electronic and catalytic cycle of 2. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Source Title: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
URI: https://scholarbank.nus.edu.sg/handle/10635/228689
ISSN: 1434-1948
1099-0682
DOI: 10.1002/ejic.201301598
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