Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate
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https://figshare.com/articles/dataset/Solid_State_Synthesis_of_Molybdenum_and_Tungsten_Porphyrins_and_Aerial_Oxidation_of_Coordinated_Benzenethiolate_to_Benzenesulfonate/2517433
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资源简介：
A new route is developed for the synthesis of molybdenum
and tungsten
porphyrins using [M(NO)2py2Cl2] (M
= Mo, W) as the metal source and TPP (dianion of 5,10,15,20-meso-tetraphenylporphyrin) in the benzoic acid melt. Complexes
[MoVO(TPP)(OOCPh)] (1) and [WVO(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 MoV–SPh bond to yield [MoIVO(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 [MoVO(TPP)(O3SPh)] (4). 2 undergoes similar aerial
oxidation chemistry albeit slowly.
创建时间：
2016-02-20
