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 language | English |
|---|---|
| Pages (from-to) | 95-104 |
| Number of pages | 10 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 652 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Jun 1 2002 |
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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 journal › Article
}
TY - JOUR
T1 - 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
AU - Bitterwolf, Thomas E.
AU - Scallorn, W. Bruce
AU - Bays, J. Timothy
AU - Weiss, Callie A.
AU - Linehan, John
AU - Franz, James
AU - Poli, Rinaldo
PY - 2002/6/1
Y1 - 2002/6/1
N2 - 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.
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.
KW - Amine derivatives
KW - DFT analysis
KW - Photolysis
UR - http://www.scopus.com/inward/record.url?scp=0036605651&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0036605651&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(02)01312-8
DO - 10.1016/S0022-328X(02)01312-8
M3 - Article
AN - SCOPUS:0036605651
VL - 652
SP - 95
EP - 104
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -