Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 907, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2019.121058
Keywords
Organometallic B-12; Visible light; Titanium oxide; Rhodium modification; Duet reaction; Amide
Categories
Funding
- Japan Society for the Promotion of Science (JSPS) [JP19H02735]
- KAKENHI in Precisely Designed Catalysts with Customized Scaffolding [JP18H04265]
- Adaptable and Seamless Technology Transfer Program through Target-driven R&D (A-STEP) from the Japan Science and Technology Agency (JST) [VP30118067023]
- Cooperative Research Program of Network Joint Research Center for Materials and Devices: Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials [20193019]
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The hybrid catalyst composed of the B-12 complex and rhodium ion (Rh3+) modified titanium oxide was synthesized for the visible light-driven B-12 inspired catalytic reaction. The hybrid catalyst contains 4.93 x 10(-6) molg(-1) of the B-12 complex and 5.43 x 10(-5) molg(-1) of the Rh(III) ion on the surface of titanium oxide. Visible light irradiation (lambda >= 420 nm) of the hybrid catalyst in the presence of triethylamine (Et3N) as a sacrificial reagent showed absorption at 390 nm, typical for the Co(I) state of the B-12 complex monitored by diffuse reflectance UVevis analysis, which imply that electron transfer from the titanium oxide to Co(III) center of the B-12 complex occurred by the visible light irradiation. Benzotrichloride was converted to N,N-diethylbenzamide by the visible light irradiation catalyzed by the hybrid catalyst in air at room temperature. Both the conduction band electron and valence band hole of the catalyst were utilized for the reaction to form the amide product. The reaction mechanism of the duet reaction was proposed. (c) 2019 Elsevier B.V. All rights reserved.
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