Mechanistic studies have revealed that the isospecific polymerization of epoxides by a discrete salen cobalt(III) catalyst occurs at the surface of the undissolved, crystalline complex.
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Mechanism of Alkene Hydrofunctionalization by Oxidative Cobalt(salen) Catalyzed Hydrogen Atom Transfer.
J Am Chem Soc
January 2024
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520, United States.
Oxidative MHAT hydrofunctionalization of alkenes provides a mild cobalt-catalyzed route to forming C-N and C-O bonds. Here, we characterize relevant salen-supported cobalt complexes and their reactions with alkenes, silanes, oxidant, and solvent. These stoichiometric investigations are complemented by kinetic studies of the catalytic reaction and catalyst speciation.
View Article and Find Full Text PDFCobalt-Carbon Bonding in a Salen-Supported Cobalt(IV) Alkyl Complex Postulated in Oxidative MHAT Catalysis.
J Am Chem Soc
June 2022
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
The catalytic hydrofunctionalization of alkenes through radical-polar crossover metal hydrogen atom transfer (MHAT) offers a mild pathway for the introduction of functional groups in sterically congested environments. For M = Co, this reaction is often proposed to proceed through secondary alkylcobalt(IV) intermediates, which have not been characterized unambiguously. Here, we characterize a metastable (salen)Co(isopropyl) cation, which is capable of forming C-O bonds with alcohols as proposed in the catalytic reaction.
View Article and Find Full Text PDFAlternating Copolymerization of CO and Cyclohexene Oxide Catalyzed by Cobalt-Lanthanide Mixed Multinuclear Complexes.
Inorg Chem
June 2020
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Heteromultimetallic complexes consisting of three Co(II) ions and one lanthanide ion were synthesized and applied to the alternating copolymerization of CO and cyclohexene oxide. Unlike the conventional cobalt(III) salen complexes, the high thermal stability of the present catalyst allowed us to reach a turnover number of 13000, one of the highest values ever reported for multimetallic systems. The chain propagation was first-order to the catalyst, suggesting a cooperative behavior of the metal centers.
View Article and Find Full Text PDFPolymorphism of the dinuclear Co-Schiff base complex [Co(o-van-en)]·4CHCN (o-van-en is a salen-type ligand).
Acta Crystallogr C Struct Chem
April 2019
Department of Inorganic Chemistry, University of Zaragoza, Pedro Cerbuna 12, Zaragoza, E-50009, Spain.
Reactions of Co(OH) with the Schiff base bis(2-hydroxy-3-methoxybenzylidene)ethylenediamine, denoted H(o-van-en), under different conditions yielded the previously reported complex aqua[bis(3-methoxy-2-oxidobenzylidene)ethylenediamine]cobalt(II), [Co(CHNO)(HO)], 1, under anaerobic conditions and two polymorphs of [μ-bis(3-methoxy-2-oxidobenzylidene)ethylenediamine]bis{[bis(3-methoxy-2-oxidobenzylidene)ethylenediamine]cobalt(III)} acetonitrile tetrasolvate, [Co(CHNO)]·4CHCN, i.e. monoclinic 2 and triclinic 3, in the presence of air.
View Article and Find Full Text PDFBiomolecular Interaction, Anti-Cancer and Anti-Angiogenic Properties of Cobalt(III) Schiff Base Complexes.
Sci Rep
February 2019
Department of Marine Biotechnology, Bharathidasan University, Tiruchirappalli, 620 024, India.
Two cobalt(III) Schiff base complexes, trans-[Co(salen)(DA)](ClO) (1) and trans-[Co(salophen)(DA)](ClO) (2) (where salen: N,N'-bis(salicylidene)ethylenediamine, salopen: N,N'-bis(salicylidene)-1,2-phenylenediamine, DA: dodecylamine) were synthesised and characterised using various spectroscopic and analytical techniques. The binding affinity of both the complexes with CT-DNA was explored adopting UV-visible, fluorescence, circular dichroism spectroscopy and cyclic voltammetry techniques. The results revealed that both the complexes interacted with DNA via intercalation as well as notable groove binding.
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