title: Solid-state synthesis of molybdenum and tungsten porphyrins and aerial oxidation of coordinated benzenethiolate to benzenesulfonate.
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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
authors.forename: Goutam
authors.initials: G
authors.lastname: Nandi
authors.forename: Sabyasachi
authors.initials: S
authors.lastname: Sarkar
mesh_terms: D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry; D014414:Tungsten / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D009942:Organometallic Compounds; D010636:Phenols; D013438:Sulfhydryl Compounds; D013451:Sulfonic Acids; C042983:thiophenol; D008982:Molybdenum; D014414:Tungsten