The reaction of a copper complex bearing iminosemiquinone ligands with a CF3(+) source provides an unprecedented Cu(II)-CF3 complex through ligand-based oxidation. Reactivity of this complex leads to nucleophilic trifluoromethylation of the ligand, suggesting an electronic interplay that results in a formal umpolung of the initial CF3(+).
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http://dx.doi.org/10.1039/c4cc04487h | DOI Listing |
Dalton Trans
November 2022
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, 781039, Assam, India.
The tridentate pincer ligand [L] with the ONS donor set was generated by cleaving the disulfane linkage of the pristine redox-active HSar ligand during the complexation reaction with Co(II) and Mn(II) salts in the presence of air and EtN. X-ray crystal structure analysis of the Co complex (1) and Mn complex (2) revealed that both the complexes were neutral in charge and six-coordinate with the meridional coordination of the two pincer [L] ligands. The Co ion was in the trivalent state, while the Mn ion was in the tetravalent state.
View Article and Find Full Text PDFInorg Chem
September 2021
H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
A series of thorium(IV) complexes featuring the redox-active 4,6-di--butyl--(2,6-di-isopropylphenyl)--iminobenzoquinone (iq) ligand family have been synthesized and characterized. The neutral iminoquinone ligand was used to generate Th(iq)Cl(dme) () and Th(iq)Cl (), both of which show dative bonds between the thorium(IV) ion and the ligands. One electron reduction of the ligand forms the unique tris(iminosemiquinone) complex, Th(isq)Cl (), which features a radical in each ligand.
View Article and Find Full Text PDFChem Commun (Camb)
February 2021
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, 781039, Assam, India.
An elusive aminyl radical and an iminosemiquinone radical-coordinated square pyramidal Cu(ii) complex (1) have been isolated by the reaction between the noninnocent ligand HL and Cu(ClO)·6HO in the presence of EtN and air as the sole oxidant. The geometry and electronic structure of the complex were concluded by X-ray crystallography, magnetic and EPR measurements, and density functional theory (DFT) calculations. This work reports the first crystallographic example of the two different types of radicals co-existing in a stable complex.
View Article and Find Full Text PDFRSC Adv
June 2020
Nicolaus Copernicus University, Faculty of Chemistry 87-100 Torun Poland.
A new Ni(ii) complex, was synthesized from the reaction of a non-innocent -aminophenol ligand, and Ni(OAc). The crystal structure of NiL (in which, IS stands for iminosemiquinone radical ligand with cyanide (shown by N in NIS) substituent on phenolate rings) exhibits the square planar environment of Ni(ii). The complex has been crystalized in the monoclinic system and Ni(ii) was surrounded by two oxygen and two nitrogen atoms of two ligands.
View Article and Find Full Text PDFDalton Trans
September 2019
Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
A tridentate benzoxazole-containing aminophenol ligand NNO was coordinated to Co and V metal centers and the electronic structure of the resultant complexes characterized by both experimental and theoretical methods. The solid state structure of the Co complex exhibits a distorted octahedral geometry with two tridentate ligands bound in meridional fashion, and coordination-sphere bond lengths consistent with a Co(iii) oxidation state. EPR and magnetic data support a S = 1/2 ground state, and a formal electronic description of Co(iii)(NNO)(NNO) where NNO corresponds to an amidophenoxide and NNO to the iminosemiquinone redox level.
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