Neutral and Zwitterion ic Low-Coordinate Titani urn Complexes Bearing the Terminal Phosphinidene Functionality. Structural, Spectroscopic, Theoretical, and Catalytic Studies Addressing the Ti—P Multiple Bond.
α-Hydrogen abstraction and α-hydrogen migration reactions yield novel titanium(IV) complexes bearing terminal phosphinidene ligands. Via an α-H migration reaction, the phosphinidene (nacnac)TiP[Trip](CHBu) (nacnac = [Ar]NC(Bu)CHC(Bu)N[Ar], Ar = 2,6-(CHMe)CH, Trip = 2,4,6-PrCH) was prepared by the a...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 41; pp. 13575 - 13586 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
10/18/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=23177948&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 23177948 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: 10/18/2006 vid: 128 iid: 41 pid: 997 pub: American Chemical Society artinfo: ui: 23177948 10.1021/ja064853o ppf: 13575 ppct: 11 formats: tig: atl: Neutral and Zwitterion ic Low-Coordinate Titani urn Complexes Bearing the Terminal Phosphinidene Functionality. Structural, Spectroscopic, Theoretical, and Catalytic Studies Addressing the Ti—P Multiple Bond. aug: au: Guangyu Zhao Basuli, Falguni Kilgore, Uriah J. Fan, Hongiun Aneetha, Halikhedkar Huffman, John C. Gang Wu Mindiola, Daniel J. affil: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405 Department of Chemnistry, Queen's University, 90 Bader Lane, Kingston, Ontario, K7L3N6 Canada su: Titanium compounds Phosphorus compounds Complex compounds Ligands (Chemistry) Chemical structure Catalysis Chemical bonds sug: subj: Titanium compounds Phosphorus compounds Complex compounds Ligands (Chemistry) Chemical structure Catalysis Chemical bonds ab: α-Hydrogen abstraction and α-hydrogen migration reactions yield novel titanium(IV) complexes bearing terminal phosphinidene ligands. Via an α-H migration reaction, the phosphinidene (nacnac)TiP[Trip](CHBu) (nacnac = [Ar]NC(Bu)CHC(Bu)N[Ar], Ar = 2,6-(CHMe)CH, Trip = 2,4,6-PrCH) was prepared by the addition of the primary phosphide LiPH[Trip] to the nucleophilic alkylidene triflato complex (nacnac)TiCHBu(OTf), while α-H abstraction was promoted by the addition of LiPH[Trip] to the dimethyl triflato precursor (nacnac)Ti(CH)(OTf) to afford (nacnac)TiP[Trip](cH). Treatment of (nacnac)TiP[Trip](CH) with B(CF) induces methide abstraction concurrent with formation of the first titanium(lV) phosphinidene zwitterion complex (nacnac)TiP[Trip]{CHB(CF)} Complex (nacnac)-TiP[Trip]{CHB(CF)} [2 + 2] cycloadds readily PhCCPh to afford the phosphametallacyclobutene [(nacnac)Ti(p[Trip]PhCCPh)][CHB(CF)]. These titanium(IV) phosphinidene complexes possess the shortest TiP bonds reported, have linear phosphinidene groups, and reveal significantly upfielded solution P NMR spectroscopic resonances for the phosphinidene phosphorus. Solid state P NMR spectroscopic data also corroborate with all three complexes possessing considerably shielded chemical shifts for the linear and terminal phosphinidene functionality. In addition, high-level DFT studies on the phosphinidenes suggest the terminal phosphinidene linkage to be stabilized via a pseudo TiP bond. Linearity about the TiPC linkage is highly dependent on the sterically encumbering substituents protecting the phosphinidene. Complex (nacnac)TiP[Trip]{CHB(CF)} can catalyze the hydrophosphination of PhCCPh with HPPh to produce the secondary vinylphosphine HP[Ph]PhCCHPh. In addition, we demonstrate that this zwitterion is a powerful phospha-Staudinger reagent and can therefore act as a carboamination precatalyst of diphenylacetylene with aldimines. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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