Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds

Thomas E. Bitterwolf, J. Timothy Bays, Bruce Scallorn, Callie Ann Weiss, Michael W. George, Ian G. Virrels, John Linehan, Clement R. Yonker

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Photolysis of fresh samples of the η3-allyl compounds [(η5-C5H5)Mo(CO)23-C3H5)] or [(η5-C5H5)Mo(CO)23C3H4CH3)] in a Nujol matrix at ca. 90 K 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 [(η5-C5H5)Mo(CO)23-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 [(η5-C5H5)Mo(H)(CO) (η4-C4H6)] was observed along with CO loss. Time-resolved IR studies of the flash photolysis of [(η5-C5H5)Mo(CO)23 -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 [(η5-C5H5)Mo(CO)(n-heptane) (η3-C3H5)]. When [(η5-C5H5)Mo(CO)23-C3H5)] was dissolved in supercritical ethylene and photolyzed, [(η5-C5H5)Mo(CO)(C2H4) (η3C3H5)] was formed. A mechanism involving two distinct excited states is proposed to account for the photoreversible endo/exo transformations.

Original languageEnglish
Pages (from-to)2619-2624
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Issue number10
Publication statusPublished - 2001

Fingerprint

Molybdenum compounds
Carbon Monoxide
Photolysis
Allyl Compounds
Wavelength
Excited states

Keywords

  • Allyl ligands
  • Matrix isolation
  • Molybdenum
  • Photochemistry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Bitterwolf, T. E., Bays, J. T., Scallorn, B., Weiss, C. A., George, M. W., Virrels, I. G., ... Yonker, C. R. (2001). Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds. European Journal of Inorganic Chemistry, (10), 2619-2624.

Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds. / Bitterwolf, Thomas E.; Bays, J. Timothy; Scallorn, Bruce; Weiss, Callie Ann; George, Michael W.; Virrels, Ian G.; Linehan, John; Yonker, Clement R.

In: European Journal of Inorganic Chemistry, No. 10, 2001, p. 2619-2624.

Research output: Contribution to journalArticle

Bitterwolf, TE, Bays, JT, Scallorn, B, Weiss, CA, George, MW, Virrels, IG, Linehan, J & Yonker, CR 2001, 'Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds', European Journal of Inorganic Chemistry, no. 10, pp. 2619-2624.
Bitterwolf TE, Bays JT, Scallorn B, Weiss CA, George MW, Virrels IG et al. Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds. European Journal of Inorganic Chemistry. 2001;(10):2619-2624.
Bitterwolf, Thomas E. ; Bays, J. Timothy ; Scallorn, Bruce ; Weiss, Callie Ann ; George, Michael W. ; Virrels, Ian G. ; Linehan, John ; Yonker, Clement R. / Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds. In: European Journal of Inorganic Chemistry. 2001 ; No. 10. pp. 2619-2624.
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abstract = "Photolysis of fresh samples of the η3-allyl compounds [(η5-C5H5)Mo(CO)2 (η3-C3H5)] or [(η5-C5H5)Mo(CO)2 (η3C3H4CH3)] in a Nujol matrix at ca. 90 K 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 [(η5-C5H5)Mo(CO)2 (η3-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 [(η5-C5H5)Mo(H)(CO) (η4-C4H6)] was observed along with CO loss. Time-resolved IR studies of the flash photolysis of [(η5-C5H5)Mo(CO)2 (η3 -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 [(η5-C5H5)Mo(CO)(n-heptane) (η3-C3H5)]. When [(η5-C5H5)Mo(CO)2 (η3-C3H5)] was dissolved in supercritical ethylene and photolyzed, [(η5-C5H5)Mo(CO)(C2H4) (η3C3H5)] was formed. A mechanism involving two distinct excited states is proposed to account for the photoreversible endo/exo transformations.",
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AU - Bays, J. Timothy

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AU - Weiss, Callie Ann

AU - George, Michael W.

AU - Virrels, Ian G.

AU - Linehan, John

AU - Yonker, Clement R.

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