Formation of Rhodium Carbonyl Cluster Thiolates with Concomitant H2 evolution
(2001) In Journal of Organometallic Chemistry 623(1-2). p.65-73- Abstract
- Reaction of [Rh6(CO)15(NCMe)] with p-thiocresol [(4-Me)C6H4SH] leads to the formation of [Rh2(CO)4(μ-SC6H4CH3)2] as the main product along with a small amount of [Rh6(CO)16]. An approximately 30-fold excess of the thiol is required in order to obtain a good yield of the thiolate-bridged dimer while reaction of [Rh4(CO)12] with an excess of p-thiocresol leads to an apparently clean conversion to the dimeric Rh(I) complex. Mass spectrometric measurements show that the latter reaction involves evolution of H2, and CO evolution is indicated by the retardation of the reaction in CO saturated solution; these results suggest the following reaction stoichiometry: [Rh4(CO)12]+4RSH→2[Rh2(CO)4(μ-SR)2]+2H2+4CO. Kinetic measurements show that the... (More)
- Reaction of [Rh6(CO)15(NCMe)] with p-thiocresol [(4-Me)C6H4SH] leads to the formation of [Rh2(CO)4(μ-SC6H4CH3)2] as the main product along with a small amount of [Rh6(CO)16]. An approximately 30-fold excess of the thiol is required in order to obtain a good yield of the thiolate-bridged dimer while reaction of [Rh4(CO)12] with an excess of p-thiocresol leads to an apparently clean conversion to the dimeric Rh(I) complex. Mass spectrometric measurements show that the latter reaction involves evolution of H2, and CO evolution is indicated by the retardation of the reaction in CO saturated solution; these results suggest the following reaction stoichiometry: [Rh4(CO)12]+4RSH→2[Rh2(CO)4(μ-SR)2]+2H2+4CO. Kinetic measurements show that the reaction proceeds in three stages which are proposed to involve two rapid pre-equilibria and a final irreversible and relatively slow conversion to the products. The crystal and molecular structure of [Rh2(CO)4(μ2-SC6H4CH3)2] is reported. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/959193
- author
- Kiriakidou-Kazemifar, Nitsa LU ; Haukka, Matti ; Pakkanen, Tapani ; Tunik, Sergey and Nordlander, Ebbe LU
- organization
- publishing date
- 2001
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Rhodium, Thiol, Cluster, Hydrodesulfurization, Mechanism
- in
- Journal of Organometallic Chemistry
- volume
- 623
- issue
- 1-2
- pages
- 65 - 73
- publisher
- Elsevier
- external identifiers
-
- scopus:0035971028
- ISSN
- 0022-328X
- DOI
- 10.1016/S0022-328X(00)00657-4
- language
- English
- LU publication?
- yes
- id
- 2c51266a-b903-43a3-85eb-44efd699a687 (old id 959193)
- date added to LUP
- 2016-04-01 15:43:40
- date last changed
- 2022-01-28 06:49:23
@article{2c51266a-b903-43a3-85eb-44efd699a687, abstract = {{Reaction of [Rh6(CO)15(NCMe)] with p-thiocresol [(4-Me)C6H4SH] leads to the formation of [Rh2(CO)4(μ-SC6H4CH3)2] as the main product along with a small amount of [Rh6(CO)16]. An approximately 30-fold excess of the thiol is required in order to obtain a good yield of the thiolate-bridged dimer while reaction of [Rh4(CO)12] with an excess of p-thiocresol leads to an apparently clean conversion to the dimeric Rh(I) complex. Mass spectrometric measurements show that the latter reaction involves evolution of H2, and CO evolution is indicated by the retardation of the reaction in CO saturated solution; these results suggest the following reaction stoichiometry: [Rh4(CO)12]+4RSH→2[Rh2(CO)4(μ-SR)2]+2H2+4CO. Kinetic measurements show that the reaction proceeds in three stages which are proposed to involve two rapid pre-equilibria and a final irreversible and relatively slow conversion to the products. The crystal and molecular structure of [Rh2(CO)4(μ2-SC6H4CH3)2] is reported.}}, author = {{Kiriakidou-Kazemifar, Nitsa and Haukka, Matti and Pakkanen, Tapani and Tunik, Sergey and Nordlander, Ebbe}}, issn = {{0022-328X}}, keywords = {{Rhodium; Thiol; Cluster; Hydrodesulfurization; Mechanism}}, language = {{eng}}, number = {{1-2}}, pages = {{65--73}}, publisher = {{Elsevier}}, series = {{Journal of Organometallic Chemistry}}, title = {{Formation of Rhodium Carbonyl Cluster Thiolates with Concomitant H2 evolution}}, url = {{http://dx.doi.org/10.1016/S0022-328X(00)00657-4}}, doi = {{10.1016/S0022-328X(00)00657-4}}, volume = {{623}}, year = {{2001}}, }