NDLI: On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes $[\{Rh(μ-SH)(CO)(PR_{3})\}_{2}]$

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On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes $[\{Rh(μ-SH)(CO)(PR_{3})\}_{2}]$

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On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes $[\{Rh(μ-SH)(CO)(PR_{3})\}_{2}]$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Pérez-torrente, Jesús J. Jiménez, M. Victoria Fabra, María J. Oro, Luis A. Hernandez-gruel, Marc A. F. Lahoz, Fernando J.
Description	Author Affiliation: Pérez-Torrente JJ ( Departamento de Química Inorgánica, Instituto Universitario de Catálisis Homogénea, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-C.S.I.C., 50009-Zaragoza, Spain. perez@unizar.es)
Abstract	Several bis(hydrosulfido)-bridged dinuclear rhodium(I) compounds, $[\{Rh(μ-SH)(L)_{2}\}_{2}],$ have been prepared from rhodium(I) acetylacetonato complexes, $[Rh(acac)(L)_{2}],$ and $H_{2}S(g).$ Reaction of $[Rh(acac)\{P(OPh)_{3}\}_{2}]$ with $H_{2}S(g)$ affords the dinuclear bis(hydrosulfido)-bridged compound $[\{Rh(μ-SH)\{P(OPh)_{3}\}_{2}\}_{2}]$ (1). However, reaction of complexes $[Rh(acac)(CO)(PR_{3})]$ with $H_{2}S(g)$ gives the dinuclear compound $[\{Rh(μ-SH)(CO)(PR_{3})\}_{2}]$ (R=Cy, 2; R=Ph, 4) and the trinuclear cluster $[Rh_{3}(μ-H)(μ_{3}-S)_{2}(CO)_{3}(PR_{3})_{3}]$ (R=Cy, 3; R=Ph, 5). The selective synthesis of both type of compounds has been carried out by control of the $H_{2}S(g)$ concentration in the reaction media. The trinuclear hydrido–sulfido cluster $[Rh_{3}(μ-H)(μ_{3}-S)_{2}(CO)_{3}(PPh_{3})_{3}]$ (5) has been also obtained by reaction of $[\{Rh(μ-SH)(CO)(PPh_{3})\}_{2}]$ (4) with $[Rh(acac)(CO)(PPh_{3})],$ proceeding through the trinuclear hydrosulfido–sulfido intermediate $[Rh_{3}(μ_{3}-SH)(μ_{3}-S)(CO)_{3}(PPh_{3})_{3}].$ The molecular structures of complexes 1 and 3 have been determined by X-ray diffraction methods. Compound 1 is stable in solution, but complexes 2 and 4 slowly transform in solution into the trinuclear hydrido–sulfido clusters 3 and 5, respectively, with the release of $H_{2}S(g)$ in a reversible way. $^{1}H NMR$ kinetic experiments for the transformation of 4 into 5 have revealed that this transformation follows second-order-type kinetic. The following activation parameters, $ΔH^{≠}=24±3 kJ mol^{−1}$ and of $ΔS^{≠}=−223±8 J K^{−1} mol^{−1},$ have been calculated from the determination of the second-order rate constants in the temperature range 30–45 °C. The large negative value of the activation entropy is consistent with an associative character of the rate-determining step. A plausible multistep mechanism based on the chemical behaviour of hydrosulfido–metal complexes and compatible with the kinetic behaviour has been proposed.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	45
Volume Number	15
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2009-11-16
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Bridged Compounds Chemistry Chemical Synthesis Coordination Complexes Rhodium Sulfhydryl Compounds Catalysis Crystallography, X-Ray Models, Molecular Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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