Photochemical intermediates of trans-Rh(CO)L2Cl where L = PMe3, PBu3, and i-Pr2HN and cis-Rh(CO2)(i-Pr2HN)Cl in frozen organic glasses

Thomas E. Bitterwolf, W. Bruce Scallorn, J. Timothy Bays, Callie A. Weiss, John Linehan, James Franz, Rinaldo Poli

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2 (i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr > 400 nm) and 2 (350 <λirr <400 nm) give new species, A, with carbonyl stretching bands slightly the parents bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be converted to 1 by either back potholysis or annealing. Compound 3 undergoes photochemical CO-loss to form tow isomeric photoproducts. Comparison of the carbonyl stretching frequencies of phosphine and ammine derivatives and photoproducts made it possible to eliminate PR3 loss as the source of A. DFT calculations suggest that A may be a non-planar, triplet excited state of 1 or 2. DFT calculations also support the assignment of B to cis-Rh(CO)(PMe3)2Cl.

Original languageEnglish
Pages (from-to)95-104
Number of pages10
JournalJournal of Organometallic Chemistry
Volume652
Issue number1-2
DOIs
Publication statusPublished - Jun 1 2002

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Photolysis
Carbon Monoxide
Glass
photolysis
glass
Annealing
Discrete Fourier transforms
Stretching
annealing
ammines
phosphine
matrices
Excited states
phosphines
Derivatives
energy
products
excitation

Keywords

  • Amine derivatives
  • DFT analysis
  • Photolysis

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Photochemical intermediates of trans-Rh(CO)L2Cl where L = PMe3, PBu3, and i-Pr2HN and cis-Rh(CO2)(i-Pr2HN)Cl in frozen organic glasses. / Bitterwolf, Thomas E.; Scallorn, W. Bruce; Bays, J. Timothy; Weiss, Callie A.; Linehan, John; Franz, James; Poli, Rinaldo.

In: Journal of Organometallic Chemistry, Vol. 652, No. 1-2, 01.06.2002, p. 95-104.

Research output: Contribution to journalArticle

Bitterwolf, Thomas E. ; Scallorn, W. Bruce ; Bays, J. Timothy ; Weiss, Callie A. ; Linehan, John ; Franz, James ; Poli, Rinaldo. / Photochemical intermediates of trans-Rh(CO)L2Cl where L = PMe3, PBu3, and i-Pr2HN and cis-Rh(CO2)(i-Pr2HN)Cl in frozen organic glasses. In: Journal of Organometallic Chemistry. 2002 ; Vol. 652, No. 1-2. pp. 95-104.
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abstract = "The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2 (i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr > 400 nm) and 2 (350 <λirr <400 nm) give new species, A, with carbonyl stretching bands slightly the parents bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be converted to 1 by either back potholysis or annealing. Compound 3 undergoes photochemical CO-loss to form tow isomeric photoproducts. Comparison of the carbonyl stretching frequencies of phosphine and ammine derivatives and photoproducts made it possible to eliminate PR3 loss as the source of A. DFT calculations suggest that A may be a non-planar, triplet excited state of 1 or 2. DFT calculations also support the assignment of B to cis-Rh(CO)(PMe3)2Cl.",
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AU - Bitterwolf, Thomas E.

AU - Scallorn, W. Bruce

AU - Bays, J. Timothy

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AU - Linehan, John

AU - Franz, James

AU - Poli, Rinaldo

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AB - The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2 (i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr > 400 nm) and 2 (350 <λirr <400 nm) give new species, A, with carbonyl stretching bands slightly the parents bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be converted to 1 by either back potholysis or annealing. Compound 3 undergoes photochemical CO-loss to form tow isomeric photoproducts. Comparison of the carbonyl stretching frequencies of phosphine and ammine derivatives and photoproducts made it possible to eliminate PR3 loss as the source of A. DFT calculations suggest that A may be a non-planar, triplet excited state of 1 or 2. DFT calculations also support the assignment of B to cis-Rh(CO)(PMe3)2Cl.

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