The Organometallicfac-[(CO)3Mn(H2O)3]+Aquaion: Base-Hydrolysis and Kinetics of H2O-Substitution
- 28 February 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 43 (7) , 2387-2391
- https://doi.org/10.1021/ic0352809
Abstract
The novel organometallic aqua complex [(CO)3Mn(H2O)3]+ (1+) was obtained through hydrolysis of the analogous acetone complex. IR [νCO = 2051, 1944 cm-1] and 17O NMR spectroscopy revealed the presence of a fac tricarbonyl unit. Potentiometric titrations established that the trimer [(CO)3Mn3(OH)4]- was the principal condensation product in the pH range >6 prior to slow formation of the tetramer [{(CO)3Mn}(OH)]4. Water exchange in 1+, determined by NMR line broadening as kex = 19 ± 4 s-1 at 298 K, is four orders faster than with the analogous Re complex. The activation volume ΔV⧧ = −4.5 ± 0.4 cm3 mol-1 is indicative of an associatively activated (Ia) process.Keywords
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