Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/8703
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dc.contributor.authorWhite, JMen
dc.contributor.authorNg, Victor Wee Linsen
dc.contributor.authorClarke, DCen
dc.contributor.authorSmith, PDen
dc.contributor.authorTaylor, Michelle Ken
dc.contributor.authorYoung, CGen
dc.date.accessioned2011-10-19T12:22:00Z-
dc.date.issued2009-
dc.identifier.citationInorganica Chimica Acta, 362(12), p. 4570-4577en
dc.identifier.issn1873-3255en
dc.identifier.issn0020-1693en
dc.identifier.urihttps://hdl.handle.net/1959.11/8703-
dc.description.abstractRed-black [TpiPr*MoVO]₂(μ-O)(μ-MoVIO4) (1, TpiPr* = hydrobis(3-isopropylpyrazolyl)(5-isopropylpyrazolyl)borate) has been isolated as a by-product in the synthesis of NEt4[TpiPrMo(CO)3] (TpiPr = hydrotris(3-isopropylpyrazolyl)borate) and characterized by spectroscopic and X-ray crystallographic techniques. The trinuclear, mixed-valence complex contains two distorted octahedral anti-TpiPr∗MoVO centers bridged by bent oxo (Mo-O-Mo av. 158.7°) and tetrahedral κO,κO'-molybdate ligands. The complex contains a six-membered, non-planar Mo3(μ-O)3 core and two 1,2-borotropically-shifted TpiPr* ligands (with the shifted pyrazolyl trans to MoV=O). Aerial decomposition of solid NEt4[TpiPrMo(CO)3] produces sky-blue, diamagnetic TpiPrMoO(iPrpz)(iPrpzH) (2, iPrpz⁻ = 3-isopropylpyrazolate, iPrpzH = 3-isopropyl-2H-pyrazole). Molecules of 2 feature a tridentate fac-TpiPr ligand and mutually cis terminal oxo (MoO = 1.665(2) Å) and monodentate iPrpz− and iPrpzH ligands. The latter are formed by B-N bond cleavage of TpiPr. The complex can also be synthesized by reacting NEt4[TpiPrMo(CO)3] with excess 3-isopropylpyrazole and dioxygen at 100 °C. Cleavage of the B-N bond(s) of TpiPr was also observed in the formation of TpiPrMoO(SPh)(iPrpzH) (3) as a by-product in the synthesis of TpiPrMoO₂(SPh). In the monohydrate, 3 exhibits a distorted octahedral geometry defined by a tridentate fac-TpiPr ligand and mutually cis terminal oxo (MoO = 1.676(3) Å) and monodentate SPh⁻ and iPrpzH ligands. The pyrazole β-NH group is observed to participate in a hydrogen-bond to the lattice water molecule. The complex can be synthesized in high yield by reducing TpiPrMoO₂(SPh) by HSPh or PPh3 in the presence of excess 3-isopropylpyrazole.en
dc.languageenen
dc.publisherElsevier BVen
dc.relation.ispartofInorganica Chimica Actaen
dc.title1,2-Borotropic shifts and B-N bond cleavage reactions in molybdenum hydrotris(3-isopropylpyrazolyl)borate chemistry: Mixed-valence MoVIMo₂V and pyrazole-rich oxo-MoIV complexesen
dc.typeJournal Articleen
dc.identifier.doi10.1016/j.ica.2009.05.065en
dc.subject.keywordsTransition Metal Chemistryen
dc.subject.keywordsBioinorganic Chemistryen
local.contributor.firstnameJMen
local.contributor.firstnameVictor Wee Linsen
local.contributor.firstnameDCen
local.contributor.firstnamePDen
local.contributor.firstnameMichelle Ken
local.contributor.firstnameCGen
local.subject.for2008030201 Bioinorganic Chemistryen
local.subject.for2008030207 Transition Metal Chemistryen
local.subject.seo2008970103 Expanding Knowledge in the Chemical Sciencesen
local.profile.schoolSchool of Science and Technologyen
local.profile.emailmtaylo53@une.edu.auen
local.output.categoryC1en
local.record.placeauen
local.record.institutionUniversity of New Englanden
local.identifier.epublicationsrecordune-20110323-173314en
local.publisher.placeNetherlandsen
local.format.startpage4570en
local.format.endpage4577en
local.identifier.scopusid68849111607en
local.peerreviewedYesen
local.identifier.volume362en
local.identifier.issue12en
local.title.subtitleMixed-valence MoVIMo₂V and pyrazole-rich oxo-MoIV complexesen
local.contributor.lastnameWhiteen
local.contributor.lastnameNgen
local.contributor.lastnameClarkeen
local.contributor.lastnameSmithen
local.contributor.lastnameTayloren
local.contributor.lastnameYoungen
dc.identifier.staffune-id:mtaylo53en
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.identifier.unepublicationidune:8893en
dc.identifier.academiclevelAcademicen
local.title.maintitle1,2-Borotropic shifts and B-N bond cleavage reactions in molybdenum hydrotris(3-isopropylpyrazolyl)borate chemistryen
local.output.categorydescriptionC1 Refereed Article in a Scholarly Journalen
local.search.authorWhite, JMen
local.search.authorNg, Victor Wee Linsen
local.search.authorClarke, DCen
local.search.authorSmith, PDen
local.search.authorTaylor, Michelle Ken
local.search.authorYoung, CGen
local.uneassociationUnknownen
local.year.published2009en
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