Naked (CMe)M Cations (M = Sc, Ti, and V) and Their Fluoroarene Complexes.
The ionic metallocene complexes [CpM][BPh] (Cp = CMe) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contai...
| Published in: | Journal of the American Chemical Society Vol. 127; no. 41; pp. 14310 - 14320 |
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| Main Authors: | , , , , , , , , |
| Format: | Article |
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American Chemical Society
10/19/2005
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=18880632&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 18880632 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/19/2005 vid: 127 iid: 41 pid: 997 pub: American Chemical Society artinfo: ui: 18880632 10.1021/ja054544i ppf: 14310 ppct: 10 formats: tig: atl: Naked (CMe)M Cations (M = Sc, Ti, and V) and Their Fluoroarene Complexes. aug: au: Bouwkamp, Marco W. Budzelaar, Peter H. M. Gercama, Jeroen Morales, Isabel Del Hierro Wolf, Jeanette De Meetsma, Auke Troyanov, Sergei I. Teuben, Jan H. Hessen, Bart affil: Center for Catalytic Olefin Polymerization, Stratingh Institute for Chemistry and Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands. Molecular Materials, Radboud University Nzjmegen, P.O. Box 9010, 6500 GL, Nijmegen, The Netherlands. Department of Chemistry, Moscow State University, Vorobjovy Gory, 119899 Moscow, Russia. su: Metallocenes Organometallic compounds Organic compounds Cations Tetrahydrofuran Metals sug: subj: Metallocenes Organometallic compounds Organic compounds Cations Tetrahydrofuran Metals ab: The ionic metallocene complexes [CpM][BPh] (Cp = CMe) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contain one strongly distorted Cp ligand, with one (V) or two (Ti) agostic C-H...M interactions involving the CpMe groups. For Sc and Ti, these Lewis acidic species react with fluorobenzene and 1,2-difluorobenzene to yield [CpM(F-FCH)][BPh] (M = Sc, n = 2; M = Ti, n = 1) and [CpM(F-1,2 FCH)][BPh], the first examples of ,F-fluorobenzene and ,²F-1 ,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(CF)]-, both Sc and Ti form [CpM(²FC6F5)B(C6F5)3] contact ion pairs. The nature of the metal-fluoroarene interaction was studied by density functional theory (DFT) calculations and by comparison with the corresponding tetrahydrofuran (THF) adducts and was found to be predominantly electrostatic for all metals studied. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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