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 C. Linehan; Clement R. Yonker

doi:10.1002/1099-0682(200109)2001:10<2619::AID-EJIC2619>3.0.CO;2-7

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 C. Linehan, Clement R. Yonker

Research output: Journal Publication › Article › peer-review

13 Citations (Scopus)

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.

Original language	English
Pages (from-to)	2619-2624
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Issue number	10
DOIs	https://doi.org/10.1002/1099-0682(200109)2001:10<2619::AID-EJIC2619>3.0.CO;2-7
Publication status	Published - 2001
Externally published	Yes

Keywords

Allyl ligands
Matrix isolation
Molybdenum
Photochemistry

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/1099-0682(200109)2001:10<2619::AID-EJIC2619>3.0.CO;2-7

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Bitterwolf, T. E., Bays, J. T., Scallorn, B., Weiss, C. A., George, M. W., Virrels, I. G., Linehan, J. C., & Yonker, C. R. (2001). Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds. European Journal of Inorganic Chemistry, (10), 2619-2624. https://doi.org/10.1002/1099-0682(200109)2001:10<2619::AID-EJIC2619>3.0.CO;2-7

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title = "Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds",

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.",

keywords = "Allyl ligands, Matrix isolation, Molybdenum, Photochemistry",

author = "Bitterwolf, {Thomas E.} and Bays, {J. Timothy} and Bruce Scallorn and Weiss, {Callie Ann} and George, {Michael W.} and Virrels, {Ian G.} and Linehan, {John C.} and Yonker, {Clement R.}",

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T1 - Organic matrix and solution photochemical studies of (allyl)dicarbonyl(cyclopentadienyl)molybdenum compounds

AU - Bitterwolf, Thomas E.

AU - Bays, J. Timothy

AU - Scallorn, Bruce

AU - Weiss, Callie Ann

AU - George, Michael W.

AU - Virrels, Ian G.

AU - Linehan, John C.

AU - Yonker, Clement R.

PY - 2001

Y1 - 2001

N2 - 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.

AB - 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.

KW - Allyl ligands

KW - Matrix isolation

KW - Molybdenum

KW - Photochemistry

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DO - 10.1002/1099-0682(200109)2001:10<2619::AID-EJIC2619>3.0.CO;2-7

M3 - Article

AN - SCOPUS:0034800135

SN - 1434-1948

SP - 2619

EP - 2624

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 10

ER -

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

Abstract

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