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    Coordination Chemistry of [E(Idipp)]2+ Ligands (E = Ge, Sn): Metal Germylidyne [Cp*(CO)2W≡Ge(Idipp)]+ and Metallotetrylene [Cp*(CO)3W–E(Idipp)]+ Cations

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    Type
    Article
    Authors
    Lebedev, Yury cc
    Das, Ujjal
    Schnakenburg, Gregor
    Filippou, Alexander C.
    KAUST Department
    KAUST Catalysis Center (KCC)
    Date
    2017-04-12
    Online Publication Date
    2017-04-12
    Print Publication Date
    2017-04-24
    Permanent link to this record
    http://hdl.handle.net/10754/623814
    
    Metadata
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    Abstract
    The synthesis and full characterization of the NHC-stabilized tungstenochlorostannylene [Cp*(CO)3W–SnCl(Idipp)] (1Sn), the NHC-stabilized chlorogermylidyne complex [Cp*(CO)2W═GeCl(Idipp)] (2), the tungsten germylidyne complex salt [Cp*(CO)2W≡Ge(Idipp)][B(C6H3-3,5-(CF3)2)4] (3), and the cationic metallostannylene [Cp*(CO)3W–Sn(Idipp)][Al(OC(CF3)3)4] (4Sn) are reported (Idipp = 2,3-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene, Cp* = η5-C5Me5). Metathetical exchange of SnCl2(Idipp) with Li[Cp*W(CO)3] afforded selectively 1Sn. Photolytic decarbonylation of the Ge analogue [Cp*(CO)3W–GeCl(Idipp)] (1Ge) afforded the NHC-stabilized chlorogermylidyne complex (2), featuring a trigonal-planar coordinated germanium center and a W–Ge double bond (W–Ge 2.3496(5) Å). Chloride abstraction from 2 with Na[B(C6H3-3,5-(CF3)2)4] yielded the germylidyne complex salt 3, which contains an almost linear W–Ge–C1 linkage (angle at Ge = 168.7(1)°) and a W–Ge triple bond (2.2813(4) Å). Chloride elimination from 1Ge afforded the tungstenogermylene salt [Cp*(CO)3W–Ge(Idipp)][B(C6H3-3,5-(CF3)2)4] (4Ge), which in contrast to 1Ge could not be decarbonylated to form 3 despite the less strongly bound carbonyl ligands. The tin compounds 1Sn and 4Sn did not afford products bearing multiple W–Sn bonds. Treatment of 4Ge with Me2NC≡CNMe2 yielded unexpectedly the neutral germyl complex 5 containing a pendant 1-germabicyclo-[3,2,0]-hepta-2,5-diene ligand instead of the anticipated [2 + 1]-cycloaddition product at the Ge-center.
    Citation
    Lebedev YN, Das U, Schnakenburg G, Filippou AC (2017) Coordination Chemistry of [E(Idipp)]2+ Ligands (E = Ge, Sn): Metal Germylidyne [Cp*(CO)2W≡Ge(Idipp)]+ and Metallotetrylene [Cp*(CO)3W–E(Idipp)]+ Cations. Organometallics 36: 1530–1540. Available: http://dx.doi.org/10.1021/acs.organomet.7b00110.
    Sponsors
    We thank the Deutsche Forschungsgemeinschaft (SFB813, “Chemistry at Spin Centers”) and University of Bonn for the financial support of this work. We appreciate the assistance of C. Schmidt, K. Prochnicki, and H. Spitz for recording the solution NMR spectra and A. Martens for the elemental microanalyses.
    Publisher
    American Chemical Society (ACS)
    Journal
    Organometallics
    DOI
    10.1021/acs.organomet.7b00110
    Additional Links
    http://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00110
    Relations
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    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.organomet.7b00110
    Scopus Count
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    Articles; KAUST Catalysis Center (KCC)

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