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Thermodynamic and Kinetic Studies of the Complexes W(CO)
3
(PCy
3
)
2
(L) (L = H
2
, N
2
, NCCH
3
, Pyridine, P(OMe)
3
, CO)
Article
Gonzalez, AA, Zhang, K, Nolan, SP
et al
. (1988). Thermodynamic and Kinetic Studies of the Complexes W(CO)
3
(PCy
3
)
2
(L) (L = H
2
, N
2
, NCCH
3
, Pyridine, P(OMe)
3
, CO) .
ORGANOMETALLICS,
7(12), 2429-2435. 10.1021/om00102a001
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Gonzalez, AA, Zhang, K, Nolan, SP
et al
. (1988). Thermodynamic and Kinetic Studies of the Complexes W(CO)
3
(PCy
3
)
2
(L) (L = H
2
, N
2
, NCCH
3
, Pyridine, P(OMe)
3
, CO) .
ORGANOMETALLICS,
7(12), 2429-2435. 10.1021/om00102a001
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cited authors
Gonzalez, AA; Zhang, K; Nolan, SP; de la Vega, RL; Mukerjee, SL; Hoff, CD; Kubas, GJ
authors
Lopez De La Vega, Ramon
abstract
The complexes W(CO)3(PCy3)2(L) have been studied by solution calorimetry. The enthalpies of binding (kcal/mol) of ligands to W(PCy3)2(CO)3 in toluene solution are as follows: H2, -9.9, N2, -13.5; NCCH3, -15.1; pyridine, -18.9; P(OMe)3, -26.5; CO, -30.4. Similar values are obtained in tetrahydrofuran solution. These data imply bond strengths much lower than expected from gas-phase studies. The origin of this discrepancy is attributed to the presence of the W•••H-C “agostic” interaction. This is estimated to be on the order of 10 ± 6 kcal/mol. In order to investigate the role of the “agostic” interaction in the energetics of this complex, the kinetics of reaction of W(CO)3[P(C6H11)3]2(py) and W(CO)3[P(C6D11)3]2(py) with P(OMe)3 in toluene were studied. A kinetic isotope effect, kH/kD = 1.20 ± 0.05, was observed, and verifies the importance of the “agostic” bond in ligand substitution for this complex. A mechanism is proposed that involves concerted replacement of coordinated pyridine by the three-center W•••H-C bond. © 1988, American Chemical Society. All rights reserved.
publication date
January 1, 1988
published in
ORGANOMETALLICS
Journal
Identifiers
Digital Object Identifier (DOI)
https://doi.org/10.1021/om00102a001
Additional Document Info
start page
2429
end page
2435
volume
7
issue
12