Isomerization of the osmiumtellurium cluster Os(-TeR)(CO): a kinetic and computational study

• Published in: Dalton transactions : an international journal of inorganic chemistry 2016-04, Vol.45 (16), p.7158-7162
• Main Authors: Shim, E. K. S, Leong, W. K, Li, Y.-Z, Richmond, M. G
• Format: Article
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c6dt00588h

The kinetics for the isomerization of the 50e cluster Os 3 (-TeTol- p ) 2 (CO) 10 ( 3 ), where the tellurides bridge two different OsOs edges, to one in which the tellurides bridge the same open OsOs edge ( 4 ) have been measured experimentally by 1 H NMR spectroscopy. The determined activation parameters are H = 77 9 kJ mol 1 and S = 12 28 J mol 1 K. The conversion of 3 to 4 has been computationally investigated by electronic structure calculations using the model compound Os 3 (-TeMe) 2 (CO) 10 . The computed isomerization pathway is consistent with the kinetic data and the thermodynamic preference for the product stereoisomer that possesses a slipped, eclipsed conformation for the two p -tolyl groups. The kinetics for the isomerization of the 50e cluster Os 3 (-TeTol- p ) 2 (CO) 10 ( 3 ), where the tellurides bridge two different OsOs edges, to one in which the tellurides bridge the same open OsOs edge ( 4 ) have been measured experimentally by 1 H NMR spectroscopy.