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dc.contributor.authorAlberola Catalán, Antonio
dc.contributor.authorLlusar, Rosa
dc.contributor.authorVicent Barrera, Cristian
dc.contributor.authorAndrés, Juan
dc.contributor.authorPolo Ortiz, Victoriano
dc.contributor.authorGómez García, Carlos J.
dc.date.accessioned2013-09-24T12:34:11Z
dc.date.available2013-09-24T12:34:11Z
dc.date.issued2008-03
dc.identifier.citationInorganic Chemistry, 47, 9, p. 3661–3668ca_CA
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10234/73206
dc.description.abstractThe synthesis, crystal structure, and magnetic properties of [Mo3(CoCO)Se4(dmpe)3Cl3] (1), [Mo3(CoCl)Se4(dmpe)3Cl3] (2), and [Mo3(CoCl)Se4(dmpe)3Cl3](TCNQ) ([2](TCNQ)) (dmpe = 1,2-bis(dimethylphosphanyl)ethane; TCNQ = 7,7,8,8-tetracyanoquinomethane) cubane-type complexes with 16, 15, and 14 metal electrons, respectively, are reported. These compounds complete the series of cobalt-containing Mo3CoQ4 (Q = S, Se) cubane-type complexes, which allows a complete analysis of the consequences of replacing the inner chalcogen and the metal electron count on the structural, magnetic, and electrochemical properties. The experimental evidence is theoretically supported and rationalized on the basis of density-functional theory calculations. For the 15-metal electron [Mo3(CoCl)Se4(dmpe)3Cl3] complex with S = 1/2, both electron paramagnetic resonance and theoretical studies give support to a spin density mainly located on the heteroatom. The nature of the highest occupied molecular orbital upon chalcogen exchange within the Mo3CoQ4 (Q = S, Se) series remains essentially unchanged, whereas the nature of the ligand attached to Co (Cl or CO) results in a different ordering of the molecular orbital scheme. This behavior is explained by the absence of backdonation between an occupied d orbital of Co to an empty π* Cl orbital, to yield frontier orbitals that differ from those of previous models.ca_CA
dc.format.extent7 p.ca_CA
dc.language.isoengca_CA
dc.publisherAmerican Chemical Societyca_CA
dc.rightsCopyright © 2008 American Chemical Societyca_CA
dc.titleSynthesis and Molecular and Electronic Structures of a Series of Mo3CoSe4 Cluster Complexes with Three Different Metal Electron Populationsca_CA
dc.typeinfo:eu-repo/semantics/articleca_CA
dc.identifier.doihttp://dx.doi.org/10.1021/ic7022083
dc.rights.accessRightsinfo:eu-repo/semantics/restrictedAccessca_CA
dc.relation.publisherVersionhttp://pubs.acs.org/doi/abs/10.1021/ic7022083ca_CA


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