Synthesis and Characterization of Five New Tetrakis(N-phenylacetamidato) Dirhodium(II) Amine Complexes and One Molybdenum Cofactor Described Crystallographically

• Main Author: Harris, Cragin K
• Format: Others
• Language: English
• Published: Digital Commons @ East Tennessee State University 2015
• Subjects: X-ray Crystallography; Dirhodium(II); Phenylacetamide; Molybdenum; Cofactor; Catalyst; Imidazole; 4; 4-Bipyridine; 1; 5-Naphthyridine; Inorganic Chemistry
• Online Access: https://dc.etsu.edu/etd/2525; https://dc.etsu.edu/cgi/viewcontent.cgi?article=3848&context=etd

Six new crystal structures were determined using a Rigaku Mercurcy 375/MCCD(XtaLab mini) diffractometer. The structure of a molybdenum cofactor was solved resulting in an R1 (R1 = Σ ||Fo| - |Fc|| / Σ |Fo|) of 3.61% despite the presence of a disordered DMSO molecule. New Tetrakis(N-phenylacetamidato) Dirhodium(II) complexes were synthesized and characterized. Two 2,2-cis-[Rh2(NPhCOCH3)4]•(C3H4N2)x where x= 1 or 2 were successfully crystallized and solved with R1 values below 5%. Additional studies were conducted via NMR to observe formation of both products. Three potential catalysts were synthesized starting with 3,1-[Rh2(NPhCOCH3)4]. The resulting compounds were a mono adduct 3,1-[Rh2(NPhCOCH3)4]•(C3H4N2), and two dimer of dimers complexes with amine bridges 3,1-[Rh2(NPhCOCH3)4]2•(C8H6N2) and 3,1-[Rh2(NPhCOCH3)4]2•(C10H8N2). All three complexes were crystallized and solved with R1 values less than 10%. Additional NMR studies were conducted to elucidate solid and solution phase structures and to determine the possibility of additional amine bonds forming.