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Kinetics of Carbon Monoxide Exchange in Chloro and Bromo Carbonyl Complexes of Palladium(II) and Platinum(II)

Olsson, Anders; Roodt, Andreas; Bojczuk, Maria; Heaton, Brian and Elding, Lars Ivar LU (1994) In Journal of the Chemical Society. Dalton Transactions 1994(24). p.2726-3723
Abstract (Swedish)
Carbonyl exchange between [MX3(13CO)]–(MX = PdCl, PtCl or PtBr) and 12CO has been studied by IR and 13C NMR spectroscopies as a function of temperature. The exchange is first-order in both CO and complex concentration, and the activation entropies are negative, suggesting an associative reaction mechanism. There is a small solvent effect, but no chloride dependence. Activation parameters and rate constants, in the order ΔH‡/kJ mol–1, ΔS‡/J K–1 mol–1kes298/dm3 mol–1 s–1, are for [PdCl3(CO)]– 60 ± 8, –47 ± 30, 0.57 ± 0.07; for [PtCl3(CO)]– 60 ± 7, –91 ± 22, (3.3 ± 0.3)× 10–3 and for [PtBr3(CO)]– 49 ± 6, –104 ± 19, (6.0 + 0.2)× 10 –2(95% confidence interval). This is three to six orders of magnitude slower than ethene exchange in analogous... (More)
Carbonyl exchange between [MX3(13CO)]–(MX = PdCl, PtCl or PtBr) and 12CO has been studied by IR and 13C NMR spectroscopies as a function of temperature. The exchange is first-order in both CO and complex concentration, and the activation entropies are negative, suggesting an associative reaction mechanism. There is a small solvent effect, but no chloride dependence. Activation parameters and rate constants, in the order ΔH‡/kJ mol–1, ΔS‡/J K–1 mol–1kes298/dm3 mol–1 s–1, are for [PdCl3(CO)]– 60 ± 8, –47 ± 30, 0.57 ± 0.07; for [PtCl3(CO)]– 60 ± 7, –91 ± 22, (3.3 ± 0.3)× 10–3 and for [PtBr3(CO)]– 49 ± 6, –104 ± 19, (6.0 + 0.2)× 10 –2(95% confidence interval). This is three to six orders of magnitude slower than ethene exchange in analogous ethene halide complexes.

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Abstract
Carbonyl exchange between [MX(3)((CO)-C-13)](-) (MX = PdCl, PtCl or PtBr) and (CO)-C-12 has been studied by IR and C-13 NMR spectroscopies as a function of temperature. The exchange is first-order in both CO and complex concentration, and the activation entropies are negative, suggesting an associative reaction mechanism. There is a small solvent effect. but no chloride dependence. Activation parameters and rate constants, in the order Delta H-double dagger/kJ mol(-1), Delta S-double dagger/J K-1 mol(-1), k(ex)(298)/dm(3) mol(-1) s(-1), are for [PdCl3(CO)](-) 60 +/- 8, -47 +/- 30, 0.57 +/- 0.07; for [PtCl3(CO)](-) 60 +/- 7. -91 +/- 22, (3.3 +/- 0.3) x 10(-3) and for [PtBr3(CO)](-) 49 +/- 6, -104 +/- 19, (6.0 + 0.2) x 10(-2) (95% confidence... (More)
Carbonyl exchange between [MX(3)((CO)-C-13)](-) (MX = PdCl, PtCl or PtBr) and (CO)-C-12 has been studied by IR and C-13 NMR spectroscopies as a function of temperature. The exchange is first-order in both CO and complex concentration, and the activation entropies are negative, suggesting an associative reaction mechanism. There is a small solvent effect. but no chloride dependence. Activation parameters and rate constants, in the order Delta H-double dagger/kJ mol(-1), Delta S-double dagger/J K-1 mol(-1), k(ex)(298)/dm(3) mol(-1) s(-1), are for [PdCl3(CO)](-) 60 +/- 8, -47 +/- 30, 0.57 +/- 0.07; for [PtCl3(CO)](-) 60 +/- 7. -91 +/- 22, (3.3 +/- 0.3) x 10(-3) and for [PtBr3(CO)](-) 49 +/- 6, -104 +/- 19, (6.0 + 0.2) x 10(-2) (95% confidence interval). This is three to six orders of magnitude slower than ethene exchange in analogous ethene halide complexes. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Carbon monoxide, Palladium(II), Platinum(II), Carbonyl exchange, Kinetics, IR spectroscopy, NMR spectroscopy, Reaction mechanism
in
Journal of the Chemical Society. Dalton Transactions
volume
1994
issue
24
pages
2726 - 3723
publisher
Royal Society of Chemistry
external identifiers
  • scopus:37049068941
ISSN
1472-7773
DOI
10.1039/dt9940003723
language
English
LU publication?
yes
id
6a7201d3-099e-4511-b750-733a86ee92e2
date added to LUP
2017-01-07 18:19:51
date last changed
2017-05-29 11:37:38
@article{6a7201d3-099e-4511-b750-733a86ee92e2,
  abstract     = {Carbonyl exchange between [MX(3)((CO)-C-13)](-) (MX = PdCl, PtCl or PtBr) and (CO)-C-12 has been studied by IR and C-13 NMR spectroscopies as a function of temperature. The exchange is first-order in both CO and complex concentration, and the activation entropies are negative, suggesting an associative reaction mechanism. There is a small solvent effect. but no chloride dependence. Activation parameters and rate constants, in the order Delta H-double dagger/kJ mol(-1), Delta S-double dagger/J K-1 mol(-1), k(ex)(298)/dm(3) mol(-1) s(-1), are for [PdCl3(CO)](-) 60 +/- 8, -47 +/- 30, 0.57 +/- 0.07; for [PtCl3(CO)](-) 60 +/- 7. -91 +/- 22, (3.3 +/- 0.3) x 10(-3) and for [PtBr3(CO)](-) 49 +/- 6, -104 +/- 19, (6.0 + 0.2) x 10(-2) (95% confidence interval). This is three to six orders of magnitude slower than ethene exchange in analogous ethene halide complexes.},
  articleno    = {4/03695F},
  author       = {Olsson, Anders and Roodt, Andreas and Bojczuk, Maria and Heaton, Brian and Elding, Lars Ivar},
  issn         = {1472-7773},
  keyword      = {Carbon monoxide,Palladium(II),Platinum(II),Carbonyl exchange,Kinetics,IR spectroscopy,NMR spectroscopy,Reaction mechanism},
  language     = {eng},
  month        = {12},
  number       = {24},
  pages        = {2726--3723},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society. Dalton Transactions},
  title        = {Kinetics of Carbon Monoxide Exchange in Chloro and Bromo Carbonyl Complexes of Palladium(II) and Platinum(II)},
  url          = {http://dx.doi.org/10.1039/dt9940003723},
  volume       = {1994},
  year         = {1994},
}