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Formation of Rhodium Carbonyl Cluster Thiolates with Concomitant H2 evolution

Kiriakidou-Kazemifar, Nitsa LU ; Haukka, Matti; Pakkanen, Tapani; Tunik, Sergey and Nordlander, Ebbe LU (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)
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author
organization
publishing date
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
2008-08-18 12:45:11
date last changed
2018-05-29 09:30:05
@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},
  keyword      = {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},
  volume       = {623},
  year         = {2001},
}