Kinetics of Carbon Monoxide Exchange in Chloro and Bromo Carbonyl Complexes of Palladium(II) and Platinum(II)
(1994) In Journal of the Chemical Society. Dalton Transactions 1994(24). p.2726-3723- 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)
- 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.
(Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/6a7201d3-099e-4511-b750-733a86ee92e2
- author
- Olsson, Anders ; Roodt, Andreas ; Bojczuk, Maria ; Heaton, Brian and Elding, Lars Ivar LU
- organization
- publishing date
- 1994-12-21
- 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
- article number
- 4/03695F
- 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
- 2021-01-03 04:48:39
@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.}},
author = {{Olsson, Anders and Roodt, Andreas and Bojczuk, Maria and Heaton, Brian and Elding, Lars Ivar}},
issn = {{1472-7773}},
keywords = {{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}},
doi = {{10.1039/dt9940003723}},
volume = {{1994}},
year = {{1994}},
}