The Organometallicfac-[(CO)3Mn(H2O)3]+Aquaion: Base-Hydrolysis and Kinetics of H2O-Substitution

Autor:	Andre E. Merbach, Ulrich Prinz, Stefan Ulrich, Ulrich Koelle, Oliver Maas, Kaspar Hegetschweiler
Rok vydání:	2004
Předmět:	Inorganic Chemistry Hydrolysis Web of science Chemistry Substitution (logic) Kinetics Mineralogy Organic chemistry Physical and Theoretical Chemistry
Zdroj:	Inorganic Chemistry. 43:2387-2391
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic0352809
Popis:	The novel organometallic aqua complex [(CO)(3)Mn(H(2)O)(3)](+) (1(+)) was obtained through hydrolysis of the analogous acetone complex. IR [nu(CO) = 2051, 1944 cm(-)(1)] and (17)O NMR spectroscopy revealed the presence of a fac tricarbonyl unit. Potentiometric titrations established that the trimer [(CO)(3)Mn(3)(OH)(4)](-) was the principal condensation product in the pH range6 prior to slow formation of the tetramer [[(CO)(3)Mn](OH)](4). Water exchange in 1(+), determined by NMR line broadening as k(ex) = 19 +/- 4 s(-)(1) at 298 K, is four orders faster than with the analogous Re complex. The activation volume DeltaV(++) = -4.5 +/- 0.4 cm(3) mol(-1) is indicative of an associatively activated (I(a)) process.
Databáze:	OpenAIRE
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