The rhenium dithiodiolate, Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazol yl) borato(ethane- 1 ,2-dithiodiolato)(oxo)rheni um(V), and Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazolyl)borato(phenylethanedithiodiolato)(oxo)rhenium(V), were synthesized by reductive cyclocondensation of alkane-1,2-dithiols with Tp'Re0��� in a one pot fashion. The rhemium monothiodiolate, Hydrido-tris-(3 ,5-dimethyl- 1 -pyrazolyl) borato(ethane- 1 ,2-monothiodiolato)(oxo)rhenium(V), and Hydrido-tris-(3 ,5- dimethyl- 1 -pyrazolyl)borato(propanemonothiodiolato)(oxo)rhenium(V), were also synthesized by using the same procedure. The syn and anti isomers of rhenium phenylethanedithiodiolate and rhenium propanemonothiodiolate were characterized by using COSY, nOe, and HSQC experiments. An X-ray crystal structure of the rhenium ethanedithiodiolate was obtained, and an unusually small dihedral angle (S-C-C-S) of about 12�� was observed. The solution conformation of these compounds was investigated by using a Karplus relationship between vicinal coupling constants and dihedral angle. The dihedral angle for the ethanedithiodiolate appeared to be 38�� indicating a staggered geometry for the ring. All of these complexes failed to cyclorevert to any detectable extent at 120��C after 7 days. This observation reflects the thermal stability of rhenium dithiodiolate and monothiodiolate complexes. Energetics of ethylene addition to tetrathioperrhenate anion (ReS������) and addition of hydrogen sulfide to the alkene adduct were calculated by DFT calculation using LACVP** basis set with B3LYP functionals. The heat of reaction of ethylene addition to ReS������ was 15.4 kcal/mol, and 111.1 kcal/mol for addition of hydrogen sulfide to the alkene adduct. These results are consistent with the stability of the dithiodiolate complex toward cycloreversion reaction. Reaction of Tp'Re0��� and ethylene sulfide led to the rhenium ethanedithiolate complex both with and without acid catalysis. This observation led to a proposed multi step mechanism. / Graduation date: 2002

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--State University of New York at Binghamton, Chemistry Department, 2005. / Includes bibliographical references.