UNUSUAL KINETICS OF GAS-PHASE PROTON-TRANSFER TO MN(CO)(5)(-) AND RE(CO)(5)(-)

Citation
Aes. Miller et al., UNUSUAL KINETICS OF GAS-PHASE PROTON-TRANSFER TO MN(CO)(5)(-) AND RE(CO)(5)(-), International reviews in physical chemistry, 15(1), 1996, pp. 219-229
Citations number
70
Categorie Soggetti
Chemistry Physical
ISSN journal
0144235X
Volume
15
Issue
1
Year of publication
1996
Pages
219 - 229
Database
ISI
SICI code
0144-235X(1996)15:1<219:UKOGPT>2.0.ZU;2-7
Abstract
Rate constants for gas-phase proton transfer to Mn(CO)(5)(-), Re(CO)(5 )(-) and Cl- from reference acids and metal hydrides are determined. P roton-transfer efficiencies to Mn(CO)(5)(-) are small, and less than t he efficiencies for proton transfer to Cl-; proton-transfer efficienci es to Re(CO)(5)(-) are larger than those for Mn(CO)(5)(-), but still g enerally less than for transfer to Cl-. Proton-transfer efficiencies t o Mn(CO)(5)(-) and Re(CO)(5)(-) are substantially more dependent on th e nature of the proton donor (e.g. metal hydride versus oxy-acid). The thermoneutral proton transfer between Mn(CO)(5)(-) and (CO)-C-13-labe lled HMn(CO)(5) is particularly inefficient, occurring only in about 1 in 100 collisions. The results are discussed in view of evidence for a short lifetime of the collision complex, and the effects of electron ic and structural reorganization of Mn(CO)(5)(-) and Re(CO)(5)(-), inc luding loss of fluxionality of the metal species, which occur on proto nation.