Unprecedented Solvent-Assisted Reactivity of Hydrido W3CuS4 Cubane Clusters: The Non-Innocent Behaviour of the Cluster-Core Unit
Impact
Scholar |
Other documents of the author: Algarra, Andrés G.; Feliz Rodríguez, Marta; Fernández-Trujillo, M. Jesús; Llusar, Rosa; Safont Villarreal, Vicent Sixte; Vicent Barrera, Cristian; García Basallote, Manuel
Metadata
Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONThis resource is restricted
http://dx.doi.org/10.1002/chem.200802473 |
Metadata
Title
Unprecedented Solvent-Assisted Reactivity of Hydrido W3CuS4 Cubane Clusters: The Non-Innocent Behaviour of the Cluster-Core UnitAuthor (s)
Date
2009Publisher
WileyISSN
0947-6539Type
info:eu-repo/semantics/articlePublisher version
http://onlinelibrary.wiley.com/doi/10.1002/chem.200802473/abstractVersion
info:eu-repo/semantics/publishedVersionSubject
Abstract
Opening the cluster core: Substitution of the chloride ligand in the novel cationic cluster [W3CuS4H3Cl(dmpe)3]+ (see figure; dmpe=1,2-bis(dimethylphosphino)ethane) by acetonitrile is promoted by water addition. Kinetic ... [+]
Opening the cluster core: Substitution of the chloride ligand in the novel cationic cluster [W3CuS4H3Cl(dmpe)3]+ (see figure; dmpe=1,2-bis(dimethylphosphino)ethane) by acetonitrile is promoted by water addition. Kinetic and density functional theory studies lead to a mechanistic proposal in which acetonitrile or water attack causes the opening of the cluster core with dissociation of one of the CuS bonds to accommodate the entering ligand.
Reaction of the incomplete cuboidal cationic cluster [W3S4H3(dmpe)3]+ (dmpe=1,2-bis(dimethylphosphino)ethane) with CuI compounds produces rare examples of cationic heterodimetallic hydrido clusters of formula [W3CuClS4H3(dmpe)3]+ ([1]+) and [W3Cu(CH3CN)S4H3(dmpe)3]2+ ([2]2+). An unexpected conversion of [1]+ into [2]2+, which involves substitution of chloride by CH3CN at the copper centre, has been observed in CH3CN/H2O mixtures. Surprisingly, formation of the acetonitrile complex does not occur in neat acetonitrile and requires the presence of water. The kinetics of this reaction has been studied and the results indicate that the process is accelerated when the water concentration increases and is retarded in the presence of added chloride. Computational studies have also been carried out and a mechanism for the substitution reaction is proposed in which attack at the copper centre by acetonitrile or water causes disruption of the cubane-type core. ESI-MS experiments support the formation of intermediates with an open-core cluster structure. This kind of process is unprecedented in the chemistry of M3M′Q4 (M=Mo, W; Q=S, Se) clusters, and allows for the transient appearance of a new coordination site at the M′ site which could explain some aspects of the reactivity and catalytic properties of this kind of clusters. [-]
Is part of
Chemistry - A European Journal, 15, 18, p. 4582–4594Rights
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
This item appears in the folowing collection(s)
- QFA_Articles [829]