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RESEARCH INTERESTS
BIOINORGANIC AND COORDINATION CHEMISTRY
ORGANOMETALLIC CHEMISTRY
HOMOGENEOUS CATALYSIS
ELECTRO- AND PHOTO - CATALYSIS
DESIGNING MODEL COMPLEXES AS CATALYSTS FOR PROTON REDUCTION, CO2 REDUCTION, DRUG CARRIERS, MOLECULAR SENSORS
SMALL MOLECULE ACTIVATION AND DEVELOPING ALTERNATIVE RENEWABLE ENERGY RESOURCES
BIOMIMETIC INORGANIC CHEMISTRY
DESIGNING SELF-ASSEMBLED-MONOLAYERS-SAMS
TECHNIQUES USED
NMR
FTIR
UV-Vis
RAMAN
ELECTROCHEMISTRY
EPR
MASS SPECTROSCOPY
X-RAY STRUCTURE ANALYSIS
CHN ANALYSIS
DFT CALCULATIONS
SEM / TEM
The mono-substituted complex [Fe2(CO)5(μ-naphthalene-2-thiolate)2(P(PhOMe-p)3)] was prepared taking after the structural principles from both [NiFe] and [FeFe]-hydrogenase enzymes. Crystal structures are reported for this complex and the all carbonyl analogue. The bridging naphthalene thiolates resemble μ-bridging cysteine amino acids. One of the naphthyl moieties forms π–π stacking interactions with the terminal bulky phosphine ligand in the crystal structure and in calculations. This interaction stabilizes the reduced and protonated forms during electrocatalytic proton reduction in the presence of acetic acid and hinders the rotation of the phosphine ligand. The intramolecular π–π stabilization, the electrochemistry and the mechanism of the hydrogen evolution reaction were investigated using computational approaches.
The mono-substituted complex [Fe2(CO)5(μ-naphthalene-2-thiolate)2(P(PhOMe-p)3)] was prepared taking after the structural principles from both [NiFe] and [FeFe]-hydrogenase enzymes. Crystal structures are reported for this complex and the all carbonyl analogue. The bridging naphthalene thiolates resemble μ-bridging cysteine amino acids. One of the naphthyl moieties forms π–π stacking interactions with the terminal bulky phosphine ligand in the crystal structure and in calculations. This interaction stabilizes the reduced and protonated forms during electrocatalytic proton reduction in the presence of acetic acid and hinders the rotation of the phosphine ligand. The intramolecular π–π stabilization, the electrochemistry and the mechanism of the hydrogen evolution reaction were investigated using computational approaches.
Dalton Trans., 2018, 47, 4941-4949
Dalton Trans., 2018, 47, 4941-4949
Dalton Trans., 2019, 48, 16322-16329
Int. J. Hydr. Energ., 2023, In Press
Int. J. Hydr. Energ., 2023, In Press
Molecular hydrogen (H2) is one of the future energy carriers when replacing fossil sources. Enzymatic systems serve as an inspiration for the design of novel hydrogen evolving catalysts. Though several heterobimetallic Ru systems are known as catalysts for the hydrogen evolution reaction (HER), homogeneous mononuclear Ru systems have not been explored much. Here, a new mononuclear Ru(II) complex [cis-RuCl2(PPh3)2(κ2-TL)] (TL = 2-thiophenyl benzimidazole) possessing distorted octahedral geometry, has been synthesised and characterized as an efficient catalyst for acid-assisted hydrogen evolution by using various spectroscopic techniques as well as quantum chemical calculations. When trifluoroacetic acid is used as the proton source, the complex shows remarkable catalytic activity towards H2 production. Based on the DFT calculations, an EECC mechanism could be proposed for HER, consistent with the assignment of the observed redox transitions.
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