Substitution Behavior and Electronic Modification of Quadruply-Bonded Complexes of Molybdenum and Tungsten
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Publisher:The Ohio State University
Series/Report no.:The Ohio State University. Department of Chemistry Honors Theses; 2006
W2(mhp)4 was examined as a starting material for the synthesis of the evasive ditungsten tetracarboxylates with the following carboxylic acids: 2-thienylcarboxylic acid, benzoic acid, 9-anthracenylcarboxylic acid (Anth-9-CO2H), and 2,4,6-triisopropylbenzoic acid (TiPB). It was determined that the reaction of W2(mhp)4 and Anth-9-CO2H provides a convenient preparatory method for a W2(O2CR)4 complex. The synthesis of the series, Mo2(mhp)4-x(TiPB)x (where x = 1-4), was attempted to illustrate the ability to selectively modify the electronic structure of paddlewheel complexes. The complexes corresponding to x = 0, 1, 2, and 4 have been synthesized and UV-vis results implicate the ability to control electronic features via stepwise mhp-carboxylate ligand substitution. Dimolybdenum paddlewheel complexes were linked with both 2,5-thienyldicarboxylate and 3,4-thienyldicarboxylate as an attempt to probe the effect that linker geometry has on the electronic properties of the coupled “dimers of dimers”. The complexes were characterized via electrochemical methods and UV-vis spectroscopy. The complex, [Mo2(mhp)2(CH3CN)4][BF4]2, has been synthesized and its structure has been determined by single crystal X-ray crystallography. The reaction of this dication with a dicarboxylate salt was determined to yield a mixture of molecular triangles and squares by mass spectrometry.
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