In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2017, No. 37 ( 2017-10-10), p. 4324-4332
Abstract:
A new bis(µ‐chlorido)‐bridged cobalt(II) complex [Co 2 (µ‐Cl) 2 (HL 2 ) 4 ][CoCl 4 ] ( 1 ), where HL 2 is a silyl‐containing Schiff base, was synthesised. The structure of this compound was established by X‐ray crystallography revealing a zwitterionic form adopted by the organic ligand. The temperature dependence of the magnetic susceptibility and the field dependence of the magnetisation indicate the presence of ferromagnetic interactions between paramagnetic d 7 cobalt(II) centres ( S Co = 3/2). The exchange coupling parameter J (Co1–Co2) = +7.0 cm –1 extracted from broken‐symmetry (BS) DFT calculations agrees well with the value of +8.8 cm –1 determined from the experimental data by fitting them with the Hamiltonian . Electrochemical studies indicate that complex 1 is inefficient as a catalyst in electrochemical reduction of protons. One of the reasons is the low stability of the complex in solution. In contrast, 1 acts as an effective homogeneous (pre)catalyst in the microwave‐assisted neat oxidation of cyclohexane with aqueous t BuOOH (TBHP). The possible mechanism of catalytic oxidation and other advantages of using 1 in the oxidation of cycloalkanes are discussed.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2017.37
DOI:
10.1002/ejic.201700875
Language:
English
Publisher:
Wiley
Publication Date:
2017
detail.hit.zdb_id:
1475009-0
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