Fast and reversible insertion of carbon dioxide into zirconocene-alkoxide bonds. A mechanistic study
(2014) In Dalton Transactions 43(23). p.8894-8898- Abstract
- In two consecutive equilibria the compound (Cp*)(2)Zr(OMe)(2) undergoes insertion of CO2 to form the mono- and bis-hemicarbonates. Both equilibria are exothermic but entropically disfavoured. Magnetisation transfer experiments gave kinetic data for the first equilibrium showing that the rate of insertion is overall second order with a rate constant of 3.20 +/- 0.12 M-1 s(-1), which is substantially higher than those reported for other early transition metal alkoxides, which are currently the best homogeneous catalysts for dimethyl carbonate formation from methanol and CO2. Activation parameters for the insertion reaction point to a highly ordered transition state and we interpret that as there being a substantial interaction between the... (More)
- In two consecutive equilibria the compound (Cp*)(2)Zr(OMe)(2) undergoes insertion of CO2 to form the mono- and bis-hemicarbonates. Both equilibria are exothermic but entropically disfavoured. Magnetisation transfer experiments gave kinetic data for the first equilibrium showing that the rate of insertion is overall second order with a rate constant of 3.20 +/- 0.12 M-1 s(-1), which is substantially higher than those reported for other early transition metal alkoxides, which are currently the best homogeneous catalysts for dimethyl carbonate formation from methanol and CO2. Activation parameters for the insertion reaction point to a highly ordered transition state and we interpret that as there being a substantial interaction between the CO2 and the metal during the C-O bond formation. This is supported by DFT calculations showing the lateral attack by CO2 to have the lowest energy transition state. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/4552300
- author
- Brink, Alice ; Truedsson, Ida LU ; Fleckhaus, André LU ; Johnson, Magnus LU ; Norrby, Per Ola ; Roodt, Andreas and Wendt, Ola LU
- organization
- publishing date
- 2014
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Dalton Transactions
- volume
- 43
- issue
- 23
- pages
- 8894 - 8898
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000336800700035
- scopus:84901280849
- pmid:24796283
- ISSN
- 1477-9234
- DOI
- 10.1039/c3dt53566e
- language
- English
- LU publication?
- yes
- id
- 379cab00-37f4-4d9a-aa13-44c62d77a37b (old id 4552300)
- date added to LUP
- 2016-04-01 10:07:57
- date last changed
- 2022-01-25 20:02:56
@article{379cab00-37f4-4d9a-aa13-44c62d77a37b, abstract = {{In two consecutive equilibria the compound (Cp*)(2)Zr(OMe)(2) undergoes insertion of CO2 to form the mono- and bis-hemicarbonates. Both equilibria are exothermic but entropically disfavoured. Magnetisation transfer experiments gave kinetic data for the first equilibrium showing that the rate of insertion is overall second order with a rate constant of 3.20 +/- 0.12 M-1 s(-1), which is substantially higher than those reported for other early transition metal alkoxides, which are currently the best homogeneous catalysts for dimethyl carbonate formation from methanol and CO2. Activation parameters for the insertion reaction point to a highly ordered transition state and we interpret that as there being a substantial interaction between the CO2 and the metal during the C-O bond formation. This is supported by DFT calculations showing the lateral attack by CO2 to have the lowest energy transition state.}}, author = {{Brink, Alice and Truedsson, Ida and Fleckhaus, André and Johnson, Magnus and Norrby, Per Ola and Roodt, Andreas and Wendt, Ola}}, issn = {{1477-9234}}, language = {{eng}}, number = {{23}}, pages = {{8894--8898}}, publisher = {{Royal Society of Chemistry}}, series = {{Dalton Transactions}}, title = {{Fast and reversible insertion of carbon dioxide into zirconocene-alkoxide bonds. A mechanistic study}}, url = {{http://dx.doi.org/10.1039/c3dt53566e}}, doi = {{10.1039/c3dt53566e}}, volume = {{43}}, year = {{2014}}, }