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  • Dialkylmetal compounds  (1)
  • Pyridylphosphanes  (1)
  • amidinium ions  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1485-1494 
    ISSN: 1434-1948
    Keywords: Titanium ; Vanadium ; Polymerizations ; Diimine ; Dialkylmetal compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Mono-β-diiminato)titanium(III) and -vanadium(III) dichlorides LMCl2 [L = ArNC(R)CHC(R)NAr-] are easily accessible from the metal trichlorides and LLi in THF. The crystal structures of LVCl2 (Ar = 2,6-iPr2C6H3, R = Me) and LTiCl2 (Ar = 2,4,6-Me3C6H2, R = Me and Ar = 2,4,6-Me3C6H2, R = tBu) reveal tetrahedral metal environments. Treatment of LVCl2 with alkyllithium reagents affords surprisingly stable dialkylvanadium(III) compounds; the structure of LV(nBu)2 (Ar = 2,6-iPr2C6H3, R = Me) is similar to that of the dichloride. The corresponding dialkyltitanium(III) compounds are less stable; only the dimethyl derivatives could be obtained in pure form (from LTiCl2 and MeMgI), and only for ligands bearing 2,6-disubstituted aryl groups. The structure of LTiMe2 (Ar = 2,4,6-Me3C6H2, R = Me) is also similar to that of the dichloride. Reaction of LTiMe2 with B(C6F5)3 produces a catalyst for α-olefin polymerization, but the corresponding VIII derivatives are inactive.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Molybdenum ; Fluxionality ; Pyridylphosphanes ; Phosphane oxides ; Polydentate ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pseudo-octahedral complexes [Mo(η3-allyl)Br(CO)2(PPynPh3-n-P,N)] (Py = 2-pyridyl; n = 2, 3) and [Mo(η3-allyl)Br(CO)2(OPPymPh3-m-O,N)] (m = 1, 2, 3) undergo three different dynamic processes in solution, depending on the chelating ligand. The complexes containing PPhPy2 and PPy3 as chelating P,N-donors undergo a novel “pivoted double switch” mechanism which scrambles two equatorial coordination sites with racemization, while maintaining the identity of the phosphorus atom trans to the allyl ligand. The complexes containing 2-pyridylphosphane oxides as chelating O,N-donors undergo a nondissociative intramolecular trigonal-twist (or turnstile) rearrangement which maintains the identity of the phosphane oxide oxygen atom coordinated in an equatorial position. All the complexes containing uncoordinated pyridyls undergo a slow dissociative exchange of pyridyls without coordination site scrambling. The structure of the complex [Mo(η3-allyl)Br(CO)2(OPPy3-O,N)] has been determined by X-ray diffraction.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99363_s.pdf or from the author.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 1121-1123 
    ISSN: 0570-0833
    Keywords: amidinium ions ; carbenes ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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