Syntheses and characterization of binuclear Rh-2, Ir-2 and RhIr complexes containing dimethyl phosphonate and pyrazolate bridging ligands

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dc.contributor.authorValderrama, M
dc.contributor.authorCuevas, J
dc.contributor.authorBoys, D
dc.contributor.authorCarmona, D
dc.contributor.authorLamata, MP
dc.contributor.authorViguri, F
dc.contributor.authorAtencio, R
dc.contributor.authorLahoz, FJ
dc.contributor.authorOro, LA
dc.date.accessioned2024-01-10T13:43:42Z
dc.date.available2024-01-10T13:43:42Z
dc.date.issued1996
dc.description.abstractThe reaction of [Ir(eta(5)-C(5)Me(5))I{PO(OMe)(2)}{P(OH)OMe)(2)}] with pyrazole (Hpz) in the presence of AgPF6 gave [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}{P(OH)(OMe)(2)}(Hpz)]PF6 1. Deprotonation of 1 with sodium carbonate afforded the neutral compound [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}(2)(Hpz)] 2 which, in turn, can be deprotonated to [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)}(2)(pz)M'] (M' = Tl 3 or Na 4) by Tl(acac) (acac = acetylacetonate) or NaH, respectively. The complex [Ir(eta(5)-C(5)Me(5))I-2{P(OH)(OMe)(2)}] 5, prepared by cleaving the iodide bridges in [{Ir(eta(5)-C(5)Me(5))I}(2)(mu-I)(2)] with HPO(OMe)(2), reacted with Hpz in the presence of AgPF6 to give [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}(Hpz)(2)]PF6 6. Complexes of formulae [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)(pz)M '' L(2)][M '' L(2) = Rh(CO)(2) 7, Rh(cod) 8 or Ir(cod) 9] were prepared from 2 [Rh(acac)(CO)(2)] or from 3 and the appropriate [{M ''(cod)}(2)(mu-Cl)(2) dimer (cod = cycloocta-1,5-diene). Complex 6 reacted with [{Rh(cod)}(2)(mu-Cl)(2)] in basic medium to give [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)}(pz)(2)Rh(cod)] 10. The rhodium-thallium compound [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(2)(pz)Tl] or the in situ prepared sodium derivative [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(pz)(2)Na] reacted with the dimers [{M ''(diolefin)}(2)(mu-Cl)(2)] affording [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(2)(pz)M ''(diolefin) = [M ''(diolefin) = Ir(cod) 11 or Rh(nbd) 12] or [(eta(5)-C(5)Me(5)){PO(OMe)(2)}Rh(pz)(2)}Rh(pz)(2)M ''(diolefin)][M ''(diolefin) = Rh(cod) 13, Ir(cod) 14 or Rh(nbd) 15], respectively (nbd = bicyclo[2.2.1]hepta-2,5-diene). Related heterovalent complexes of general formula [I(eta(5)-C(5)Me(5))M{PO(OMe(2)}(2)M ''(diolefin)][M = Ir, M'(diolefin) = Rh(cod) 16 or Ir(cod) 17; M = Rh, M ''(diolefin) = Rh(cod) 18, Ir(cod) 19, or Rh(nbd) 20] have been prepared starting from the mononuclear complexes [M(eta(5)-C(5)Me(5))I{PO(OMe)(2)}{P(OH)(OMe)(2)}] (M = Ir or Rh). All the complexes have been characterized by spectroscopic of 8 by toluene-p-sulfonic acid is reported. The structures of 8 and 16 have been determined by X-ray diffraction methods. Both complexes consist of doubly bridged binuclear (C(5)Me(5))Ir-Rh(cod) species, where the Ir atoms exhibit pseudo-octahedral co-ordination and the rhodium square planar. The bridging system in 16 is formed by two identical P,O-bonded phosphonate groups, while in 8 a pyrazolate and a phosphonate ligand are bridging the metals. The intermetallic separations are 4.0445(9) (8) and 4.0928(9) Angstrom (16).
dc.fechaingreso.objetodigital2024-05-02
dc.format.extent9 páginas
dc.fuente.origenWOS
dc.identifier.doi10.1039/dt9960002877
dc.identifier.issn0300-9246
dc.identifier.urihttps://doi.org/10.1039/dt9960002877
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/78727
dc.identifier.wosidWOS:A1996UW62500041
dc.information.autorucQuímica;Valderrama M;S/I;98729
dc.issue.numero13
dc.language.isoen
dc.nota.accesocontenido parcial
dc.pagina.final2885
dc.pagina.inicio2877
dc.publisherROYAL SOC CHEMISTRY
dc.revistaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
dc.rightsacceso restringido
dc.subjectX-RAY STRUCTURE
dc.subjectPZ = PYRAZOLATE
dc.subjectCRYSTAL-STRUCTURE
dc.subject(PENTAMETHYLCYCLOPENTADIENYL)IRIDIUM COMPLEXES
dc.subjectPENTAMETHYLCYCLOPENTADIENYL-RHODIUM
dc.subjectHOMOGENEOUS CATALYSTS
dc.subjectIRIDIUM COMPLEXES
dc.subjectDERIVATIVES
dc.subjectREACTIVITY
dc.subjectSYNERGISM
dc.subject.ods12 Responsible Consumption and Production
dc.subject.odspa12 Producción y consumo responsable
dc.titleSyntheses and characterization of binuclear Rh-2, Ir-2 and RhIr complexes containing dimethyl phosphonate and pyrazolate bridging ligands
dc.typeartículo
sipa.codpersvinculados98729
sipa.indexWOS
sipa.trazabilidadCarga SIPA;09-01-2024
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