Isomerization of the osmium–tellurium cluster Os 3 (μ-TeR) 2 (CO) 10 : a kinetic and computational study

• Published in: Dalton transactions : an international journal of inorganic chemistry 2016, Vol.45 (16), p.7158-7162
• Main Authors: Shim, E. K. S., Leong, W. K., Li, Y.-Z., Richmond, M. G.
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/C6DT00588H

The kinetics for the isomerization of the 50e cluster Os 3 (μ-TeTol- p ) 2 (CO) 10 ( 3 ), where the tellurides bridge two different Os–Os edges, to one in which the tellurides bridge the same open Os⋯Os edge ( 4 ) have been measured experimentally by 1 H NMR spectroscopy. The determined activation parameters are Δ H ‡ = 77 ± 9 kJ mol −1 and Δ 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 (μ-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.