NMR Linebroadening and Contact Shift Studies of Transition Metal Complexes in Nonaqueous Solvents.

Proton nmr linebroadening studies of dimethylsulfoxide (DMSO) +3 in tris (ethylenediamine) chromium(III) (Cr(en)3 +3)-DMSO solutions were conducted between 20° and 90°C. The resulting data were interpreted using the Swift-Connick relationships. The dominant contribution to linebroadening in the temperature range of 20° - 50°C was a second - coordination sphere exchange process. Above 70°C, the dominant process was a mixture of first coordination sphere exchange process of partially +3 dissociated Cr(en) 3+3 and second coordination sphere T2m-1 relaxation. The kinetic parameters for the first and second coordination sphere processes are ΔΗ≠0 = 24 kcal/mol, k1 = 24 sec-1 and ΔΗ≠= 8.8 kcal/mol, and k1 = 2.1 x 103 sec-1 A discussion is given of the possibility of electron transfer through second coordination sphere bonding.

Level thesis:degree_level

Thesis

Year

1977

Author dc:creator

• Harris, Marvin Eugene, Jr

• Linebroadening
• Dimethylsulfoxide
• DMSO solutions
• Kinetic parameters

Repository record dc:identifier

https://digitalcommons.library.uab.edu/etd-collection/7050

OAI identifier oai:identifier

oai:digitalcommons.library.uab.edu:etd-collection-8042