A cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF2)2L2 system, but its observation has proven difficult. We have observed the UV-vis spectra of Co(dmgBF2)2L2 (1) in CH3CN under hydrogen pressures of up to 70 atm. A Co(I) compound (6a) with an exchangeable proton is eventually formed. We have determined the bond dissociation free energy and pK(a) of the new O-H bond in 6a to be 50.5 kcal/mol and 13.4, respectively, in CH3CN, matching previous reports.
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http://dx.doi.org/10.1021/ja508200g | DOI Listing |
Org Lett
November 2024
Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. China.
A regioselective radical α,γ-diphosphinylation of allylamines with secondary phosphine oxides by photoinduced cobaloxime catalysis is described. The reaction tolerates a wide range of allylamines and phosphine oxides, affording α-amino diphosphine dioxides in moderate to good yields with hydrogen evolution. The synthesis of new diphosphine monoxide and diphosphine ligands and the promising antitumor activities of products demonstrate the great potential applications of this approach in catalysis and drug discovery.
View Article and Find Full Text PDFAdv Mater
January 2025
Department of Chemical Sciences, University of Padova, Via F. Marzolo 1, Padova, 35131, Italy.
The semi-hydrogenation of acetylene in ethylene-rich gas streams is a high-priority industrial chemical reaction for producing polymer-grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H consumption, possess relatively low selectivity, and use a noble metal catalyst. Light-powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective.
View Article and Find Full Text PDFDalton Trans
October 2024
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
Three new molecular cobaloxime complexes with the general formula [ClCo(dpgH)L] (1-3), where L1 = -(4-pyridylmethyl)-1,8-naphthalimide, L2 = 4-bromo--(4-pyridylmethyl)-1,8-naphthalimide, L3 = 4-piperidin--(4-pyridylmethyl)-1,8-naphthalimide, have been synthesized and characterized by UV-Vis, multinuclear NMR, FT-IR and PXRD spectroscopic techniques. The crystal structures of all complexes have also been reported. The electrocatalytic activity of complexes is investigated under two catalysis conditions: (i) homogeneous conditions in acetonitrile using acetic acid (AcOH) as a proton source and (ii) heterogeneous conditions upon immobilization onto the surface of activated carbon cloth (CC).
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore.
The low immunogenicity of tumors, along with the abnormal structural and biochemical barriers of tumor-associated vasculature, impedes the infiltration and function of effector T cells at the tumor site, severely inhibiting the efficacy of antitumor immunotherapy. In this study, a cobaloxime catalyst and STING agonist (MSA-2)-coloaded Wurster-type covalent organic framework (Co-TB COF-M) with internal electron transfer-enhanced catalytic capacity was developed as a COF-based immune activator. The covalently anchored cobaloxime adjusts the energy band structure of TB COF and provides it with good substrate adsorption sites, enabling it to act as an electron transmission bridge between the COF and substrate in proton reduction catalytic reactions.
View Article and Find Full Text PDFJ Phys Chem A
September 2024
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States.
The photochemical decomposition of ethyl(aqua)cobaloxime, [EtCo(dmgH)HO], a vitamin B derivative model complex, was investigated to understand the mechanism of the Co-C bond scission induced by light. Upon irradiation of [EtCo(dmgH)HO], the Co-C bond undergoes homolytic scission, resulting in Et/Co(II) radical pair (RP) formation in a similar fashion observed in alkylcobalamins. The [EtCo(dmgH)HO] complex acts as a potent quencher of a wide variety of excited states in the presence of organic molecules such as benzophenone.
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