Solid-state synthesis of molybdenum and tungsten porphyrins and aerial oxidation of coordinated benzenethiolate to benzenesulfonate |
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Authors: | Nandi Goutam Sarkar Sabyasachi |
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Institution: | Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India. |
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Abstract: | A new route is developed for the synthesis of molybdenum and tungsten porphyrins using M(NO)(2)py(2)Cl(2)] (M = Mo, W) as the metal source and TPP (dianion of 5,10,15,20-meso-tetraphenylporphyrin) in the benzoic acid melt. Complexes Mo(V)O(TPP)(OOCPh)] (1) and W(V)O(TPP)(OOCPh)] (2) are isolated in almost quantitative yield. These are characterized by single-crystal X-ray structure analysis, electron paramagnetic resonance, electronic and IR spectroscopy, and magnetic moment measurements. Benzenethiol substitutes for PhCOO(-) in 1, forming an intermediate thiolato complex that responds to the intramolecular redox reaction across the Mo(V)-SPh bond to yield Mo(IV)O(TPP)] (3). Under an excess of benzenethiol, PhS(-) is coordinated to the vacant site in 3, which under aerial oxidation is oxidized to benzenesulfonate to form Mo(V)O(TPP)(O(3)SPh)] (4). 2 undergoes similar aerial oxidation chemistry albeit slowly. |
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