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Titolo:
Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds
Autore:
Bitterwolf, TE; Bays, JT; Scallorn, B; Weiss, CA; George, MW; Virrels, IG; Linehan, JC; Yonker, CR;
Indirizzi:
Univ Idaho, Dept Chem, Moscow, ID 83844 USA Univ Idaho Moscow ID USA 83844 niv Idaho, Dept Chem, Moscow, ID 83844 USA Univ Nottingham, Dept Chem, Nottingham NG7 2RD, England Univ Nottingham Nottingham England NG7 2RD , Nottingham NG7 2RD, England Pacific NW Natl Labs, Dept Chem Sci, Richland, WA 99352 USA Pacific NW Natl Labs Richland WA USA 99352 em Sci, Richland, WA 99352 USA
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 10, , anno: 2001,
pagine: 2619 - 2624
SICI:
1434-1948(200110):10<2619:OMASPS>2.0.ZU;2-C
Fonte:
ISI
Lingua:
ENG
Soggetto:
INFRARED SPECTROSCOPIC EVIDENCE; FROZEN GAS MATRICES; ALLYL COMPLEXES; 12-K; MOLYBDENUM; ASYMMETRY; MANGANESE; LIGAND; NUJOL;
Keywords:
photochemistry; matrix isolation; molybdenum; allyl ligands;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
23
Recensione:
Indirizzi per estratti:
Indirizzo: Bitterwolf, TE Univ Idaho, Dept Chem, Moscow, ID 83844 USA Univ Idaho Moscow ID USA 83844 Chem, Moscow, ID 83844 USA
Citazione:
T.E. Bitterwolf et al., "Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds", EUR J INORG, (10), 2001, pp. 2619-2624

Abstract

Photolysis of fresh samples of the eta (3)-allyl compounds [(eta (5)-C5H5)Mo(CO)(2)(eta (3)-C3H5)] or [(eta (5)-C5H5)Mo(CO)(2)(eta (3)-C3H4CH3)] in aNujol matrix at ca. 90K at a wavelength greater than 400 nm was found by IR spectroscopy to cause conversion of the endo rotamer to the exo rotamer. Photolysis of exo enriched samples of [(eta (5)-C5H5)Mo(CO)(2)(eta (3)-C3H5)] at wavelengths of between 360 and 400 nm reversed the photoconversion leading to an exo to endo conversion. At higher energies photochemical CO loss was also observed. In the case of the 2-methylallyl derivative, a photoproduct believed to be [(eta (5)-C5H5)Mo(H)(CO)(eta (4)-C4H6)] was observed along with CO loss. Time-resolved IR studies of the flash photolysis of [(eta (5)-C5H5)Mo(CO)(2)(eta (3)-C3H5)] in n-heptane confirm both endo to exo rotamer conversion and CO loss. Under these conditions, the species formed after CO loss is probably [(eta (5)-C5H5)Mo(CO)(n-heptane)(eta (3)-C3H5)]. When [(eta (5)-C5H5)Mo(CO)(2)(eta (3)-C3H5)] was dissolved in supercritical ethylene and photolyzed, [(eta (5)-C5H5)Mo(CO)(C2H4)(eta (3)-C3H5)] was formed. A mechanism involving two distinct excited states is proposed to account for the photoreversible endo/exo transformations.

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Documento generato il 01/10/20 alle ore 15:19:56