Date on Master's Thesis/Doctoral Dissertation

12-2011

Document Type

Master's Thesis

Degree Name

M.S.

Department

Chemistry

Committee Chair

Noble, Mark E.

Subject

Dimers; Reactivity (Chemistry)

Abstract

Molybdenum-sulfur complexes have developed a lot of interest in the chemistry of metal-coordinated sulfur due to their importance in biological systems and in industrial processes like catalysis. For example, in biological processes molybdenum has been recognized as a very important metal in enzymes used for nitrogen fixation for over 60 years. In this dissertation, the system of the imidodithiophosphate /l-carboxylatomolybdenum(V) dimer was studied for crystal thermolytic stability and solution reactivity. Mo2(NTo)2(S2P(OEt)2)2(µ-O2CR)(µ-SBn)(µ-SO) will be abbreviated as BnS{Mo2}SO, where R is CH3, CH2CH2CH3, C(CH3)3 or CH(OCH3)C6H5. In the crystal phase, the packing of BnS{Mo2}SO acetate allows the molecule to pair off on a close approach to allow nucleophilic attack on each other. The attack is reciprocal for each of the molecules in a pair. It is because of this juxtaposition, coupled with the inherent nucleophilic behavior of the S(O), which provides the solid state reaction at high temperatures. In solution reactions, the nucleophilic behavior of the (S)O in BnS{Mo2}SO with BnBr leads to the formation of the cation, [BnS{Mo2}SOBn]+, which undergoes either de-benzylation to give [Mo2(NTo)2(S2P(OEt)2)2(µ-O2CMe )(µ-S)(µ-SOBn)], or deesterification to give [Mo2(NTo)2(S2P=O(OEt)) (S2P(OEt)2(µ-O2CMe)(µ-SBn)(µ-SOBn)] This was a one pot synthesis of S{Mo2} SOBn unlike in the synthesis of S{Mo2} SOEt or S{Mo2} SOMe which was a two pot process.

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