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
Andrada, Diego M #
Issue Date: 2014
Series Title: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY vol:2014 issue:5 pages:818-823
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)2Ni0 (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 Ni0 (+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 (Ni0), 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.
ISSN: 1434-1948
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Non-KU Leuven Association publications
× corresponding author
# (joint) last author

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