Issue 10, 2013
From the journal:

Dalton Transactions

Bis(hydrosulfido)-bridged dinuclear rhodium(i) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru)†

Ricardo Castarlenas,a   Carmen Cunchillos,a   Daniel Gómez-Bautista,a   M. Victoria Jiménez,a   Fernando J. Lahoz,a   José R. Miranda,a   Luis A. Oro*a  and  Jesús J. Pérez-Torrente*a  

* Corresponding authors

a Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea–ISQCH, Universidad de Zaragoza–CSIC, Facultad de Ciencias, C/Pedro Cerbuna, 12, 50009 Zaragoza, Spain
E-mail: perez@unizar.es, oro@unizar.es
Fax: +34 976761143
Tel: +34 976762025

Abstract

The reaction of [Rh(μ-SH)(CO)(PPh3)]2 or [Rh(μ-SH){P(OPh)3}2]2 with [Cp*MCl2]2 (M = Rh, Ir) in the presence of NEt3 afforded the Rh3 and IrRh2 sulfido-bridged compounds [Cp*M(μ3-S)2Rh2(CO)2(PPh3)2] (M = Rh, 1; Ir, 2) and [Cp*Rh(μ3-S)2Rh2{P(OPh)3}4] (3). The reaction with [MCl2(cod)] (M = Pd, Pt), cis-[PtCl2(PPh3)2] or [(η6-C6H6)RuCl2]2 under the same experimental conditions gave [(cod)M(μ3-S)2Rh2{P(OPh)3}4] (M = Pd, 6; Pt, 7), [(cod)M(μ3-S)2Rh2(CO)2(PPh3)2] (M = Pd, 8; Pt, 9), [(PPh3)2Pt(μ3-S)2Rh2(CO)2(PPh3)2] (10) and [(η6-C6H6)Ru(μ3-S)2Rh2(CO)2(PPh3)2] (12), with PdRh2, PtRh2 and RuRh2 trimetallic cores. The aggregates derived from [Rh(μ-SH)(CO)(PPh3)]2 were isolated as a mixture of trans and cis isomers in which the trans isomer predominates. The reaction of [Rh(μ-SH){P(OPh)3}2]2 with 2 equiv. of n-BuLi at 253 K followed by addition of [Cp*IrCl2]2 gave [Cp*Ir(μ3-S)2Rh2{P(OPh)3}4] (4) and [Cp*2ClIr2(μ3-S)2Rh{P(OPh)3}2] (5) in a 3 : 2 ratio. The RuRh2 compound [(η6-C6H6)Ru(μ3-S)2Rh2{P(OPh)3}4] (11) was prepared similarly from [Rh(μ-SH){P(OPh)3}2]2 and [(η6-C6H6)RuCl2]2 using n-BuLi as a deprotonating agent. The molecular structures of compounds 3, 6, 7, 9 and 11 have been determined by X-ray analysis. The trinuclear complexes exhibit an asymmetric triangular metal core with two triply bridging sulfido ligands resulting in a distorted trigonal-bipyramidal M3(μ3-S)2 heterometallic metal–sulfur core.

Graphical abstract: Bis(hydrosulfido)-bridged dinuclear rhodium(i) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru)

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Article information

DOI
https://doi.org/10.1039/C2DT32680A
Article type
Paper
Submitted
09 Nov 2012
Accepted
03 Dec 2012
First published
03 Dec 2012

Dalton Trans., 2013,42, 3471-3481

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Bis(hydrosulfido)-bridged dinuclear rhodium(I) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru)

R. Castarlenas, C. Cunchillos, D. Gómez-Bautista, M. V. Jiménez, F. J. Lahoz, J. R. Miranda, L. A. Oro and J. J. Pérez-Torrente, Dalton Trans., 2013, 42, 3471 DOI: 10.1039/C2DT32680A

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