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 [(MoO)-O-V(TPP)(OOCPh)] (1) and [(WO)-O-V(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 [(MoO)-O-IV(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 [(MoO)-O-V(TPP)(O3SPh)] (4). 2 undergoes similar aerial oxidation chemistry albeit slowly.