paper2.pdf
Creators: name: Mamiyev, Zamin
Publisher: name: figshare
Year: 2020
Subjects: subject: 30199 Analytical Chemistry not elsewhere classified
subject: FOS: Chemical sciences
subject: FOS: Chemical sciences
subject: 30101 Analytical Spectrometry
subject: Biochemistry
subject: 30201 Bioinorganic Chemistry
subject: 30401 Biologically Active Molecules
subject: 30402 Biomolecular Modelling and Design
subject: 30601 Catalysis and Mechanisms of Reactions
subject: 30403 Characterisation of Biological Macromolecules
subject: 30301 Chemical Characterisation of Materials
subject: 39999 Chemical Sciences not elsewhere classified
subject: 30602 Chemical Thermodynamics and Energetics
subject: Cheminformatics
subject: 30404 Cheminformatics and Quantitative Structure-Activity Relationships
subject: 30603 Colloid and Surface Chemistry
subject: Computational Chemistry
subject: Crystallography
subject: 30102 Electroanalytical Chemistry
subject: Environmental Chemistry
subject: 39901 Environmental Chemistry (incl. Atmospheric Chemistry)
subject: 30604 Electrochemistry
subject: 39902 Forensic Chemistry
subject: FOS: Other medical sciences
subject: FOS: Other medical sciences
subject: 30103 Flow Analysis
subject: 30104 Immunological and Bioassay Methods
subject: Geochemistry
subject: FOS: Earth and related environmental sciences
subject: FOS: Earth and related environmental sciences
subject: 30501 Free Radical Chemistry
subject: 39903 Industrial Chemistry
subject: Inorganic Chemistry
subject: 30299 Inorganic Chemistry not elsewhere classified
subject: 30203 Inorganic Green Chemistry
subject: 30105 Instrumental Methods (excl. Immunological and Bioassay Methods)
subject: 30399 Macromolecular and Materials Chemistry not elsewhere classified
subject: 30204 Main Group Metal Chemistry
subject: 30499 Medicinal and Biomolecular Chemistry not elsewhere classified
subject: 30405 Molecular Medicine
subject: FOS: Basic medicine
subject: FOS: Basic medicine
subject: Molecular Physics
subject: NMR Spectroscopy
subject: 30302 Nanochemistry and Supramolecular Chemistry
subject: 30502 Natural Products Chemistry
subject: 30205 Non-metal Chemistry
subject: Nuclear Chemistry
subject: 30303 Optical Properties of Materials
subject: 30503 Organic Chemical Synthesis
subject: Organic Chemistry
subject: 30599 Organic Chemistry not elsewhere classified
subject: 30504 Organic Green Chemistry
subject: 39904 Organometallic Chemistry
subject: 30699 Physical Chemistry not elsewhere classified
subject: 30304 Physical Chemistry of Materials
subject: 30505 Physical Organic Chemistry
subject: 30305 Polymerisation Mechanisms
subject: 30406 Proteins and Peptides
subject: 30106 Quality Assurance, Chemometrics, Traceability and Metrological Chemistry
subject: 30701 Quantum Chemistry
subject: 30703 Reaction Kinetics and Dynamics
subject: 30108 Separation Science
subject: 30206 Solid State Chemistry
subject: 30605 Solution Chemistry
subject: 30704 Statistical Mechanics in Chemistry
subject: 30606 Structural Chemistry and Spectroscopy
subject: Stereochemistry
subject: Supramolecular Chemistry
subject: 30306 Synthesis of Materials
subject: 30207 Transition Metal Chemistry
subject: 30607 Transport Properties and Non-equilibrium Processes
subject: 30202 f-Block Chemistry

description: TiO2 is an effective and extensively employed photocatalyst,but its practical use in visible-light-mediated organic synthesis is mainlyhindered by its wide band gap energy. Herein, we have discovered that RhphotodepositedTiO2 nanoparticles selectively dehydrogenate N-heterocyclicamines with the concomitant generation of molecular hydrogen gasin an inert atmosphere under visible light (λmax = 453 nm) illumination atroom temperature. Initially, a visible-light-sensitive surface complex isformed between the N-heterocycle and TiO2. The acceptorlessdehydrogenation of N-heterocycles is initiated by direct electron transferfrom the HOMO energy level of the amine via the conduction band ofTiO2 to the Rh nanoparticle. The reaction condition was optimized byexamining different photodeposited noble metals on the surface of TiO2and solvents, finding that Rh0 is the most efficient cocatalyst, and 2-propanol is the optimal solvent. Structurally diverse N-heterocycles such as tetrahydroquinolines, tetrahydroisoquinolines, indolines,and others bearing electron-deficient as well as electron-rich substituents underwent the dehydrogenation in good to excellent yields.The amount of released hydrogen gas evinces that only the N-heterocyclic amines are oxidized rather than the dispersant. Thisdeveloped method demonstrates how UV-active TiO2 can be employed in visible-light-induced synthetic dehydrogenation of aminesand simultaneous hydrogen storage applications.