Date on Master's Thesis/Doctoral Dissertation
Noble, Mark E.
Isomerization; Reactivity (Chemistry); Dimers
The synthesis of the methyl thioperoxide-bridged dimolybdenum(V) dimer, [Mo2(NTo)2(S2P(OEt)2)2S(O2CMe)(SOMe)], was improved and the compound was structurally characterized by crystallography. The compound proved to be very stable to light and heat. The possibility of photolytic or thermolytic rearrangement of the methyl thioperoxide ligand ( -S-O-R) to a methyl sulfinyl ligand ( -S(=O)R) was investigated. These studies showed that the methyl thioperoxide compound did not produce the desired sulfinyl isomer. The photolyses produced mainly a derivative of the methyl thioperoxide compound, where a hydroxo bridge is thought to have replaced the acetate bridge. Minor products formed in general agreement with the photolysis chemistry of organic sulfenate esters (R'S-OR). The thermolyses cleaved the S-O bond, led to an intramolecular reaction and to some decomposition. The reaction of [Mo2(NTo)2(S2P(OEt)2)2S(O2CMe)(SOMe)] with HBF4 resulted in the protonation of the S-O bond's oxygen and the synthesis of a new compound, [Mo2(NTo)4(S2P(OEt)2)4S3(O2CMe)2(SOMe)](BF4).
Tuong, Chi Minh 1971-, "Isomerization, reactivity, and structural study of a thioperoxide-bridged dimolybdenum(V) dimer." (2004). Electronic Theses and Dissertations. Paper 1469.