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    Prof. Dr. Reinhold Tacke

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    Dalton Trans. 46, 13628-13659 (2017), Issue 40, 2017

    DOI: 10.1039/C7DT01297G

    Bis(amidinato)- and bis(guanidinato)silylenes and silylenes with one sterically demanding amidinato or guanidinato ligand: synthesis and reactivity

    Reinhold Tacke and Tatjana Ribeck

    This article deals with the synthesis and reactivity of the bis(amidinato)silylene [iPrNC(Ph)NiPr]2Si (5), the bis(guanidinato)silylene [iPrNC(NiPr2)NiPr]2Si (6), the mono(amidinato)silylene [DippNC(Ph)NDipp]SiNMe2 (Dipp = 2,6-diisopropylphenyl) (8) and the mono(guanidinato)silylene [DippNC(NMe2)NDipp]SiN(SiMe3)2 (9). The reactions studied include (i) nucleophilic substitutions, (ii) Lewis acid/base reactions, (iii) Brønsted acid/base reactions, (iv) oxidative additions (bond activations, small-molecule activations), (v) cycloaddition reactions with unsaturated organic substrates, (vi) reductions and (vii) radical formation by muonium addition. Silylenes 5, 6, 8 and 9 have been demonstrated to display unique reactivity profiles and to be versatile precursors for the synthesis of novel four- or five-coordinate silicon(II) and four-, five- or six-coordinate silicon(IV) complexes with unprecedented structural motifs. This article also deals with the structural characterisation of all the new silicon(II) and silicon(IV) compounds synthesised. Crystal structure analyses and 29Si NMR spectroscopic studies in the solid state and in solution were used to characterise the silicon coordination polyhedra of these compounds.

    Graphical abstract: Bis(amidinato)- and bis(guanidinato)silylenes and silylenes with one sterically demanding amidinato or guanidinato ligand: synthesis and reactivity

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    Chemistry - A European Journal" 23, 296-303 (2017) - Frontispiece

    Iron(II), cobalt(II), and zinc(II) silylene complexes: reaction of the silylene [i(PrNC(NiPr2)NiPr2]Si with FeBr2, CoBr2, NiBe2 MeOCH2CH2OMe, ZnCl2, and ZnBr2

    Authors: Johannes A. Baus, Dr. Felix M. Mück, Heidi Schneider, Prof. Dr. Reinhold Tacke

    Link:  onlinelibrary.wiley.com/doi/10.1002/chem.201780263/full

    Chem. Eur. J. 23, 296-303 (2017). more ... 

    Abstract:

    Donor-Stabilized Silylenes The chemistry of donor-stabilized silylenes has developed into one of the most actively studied research areas in molecular silicon chemistry. In their Full Paper on page 296 ff., R. Tacke et al report on the synthesis and characterization of novel transition-metal silylene complexes of FeBr2, CoBr2, NiBr2, ZnBr2, and ZnCl2 with the bis(guanidinato)silicon(II) complex [iPrNC(NiPr2)NiPr]2Si. These compounds represent very rare examples of carbonyl-free silylene complexes of 3d transition metals in the formal oxidation state +2.

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    Dalton Transactions 2017, Advance Article

    DOI: 10.1039/C6DT03264H,  Received 18 Aug 2016, Accepted 27 Sep 2016
    First published online 07 Oct 2016

    DOI: 10.1039/c6dt03264h   read more ...

    Neutral six-coordinate bis(dithiocarbamato)-silicon(IV) complexes with an SiCl2S4 skeleton

    Dr. Johannes A. Baus and Prof. Dr. Reinhold Tacke

    Graphical abstract: Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton


    Abstract

    Treatment of SiCl4 with lithium dithiocarbamates of the formula type Li[R2NCS2] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(IV) complexes [Ph2NCS2]2SiCl2 (3) and [iPr2NCS2]2SiCl2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(IV) complexes with an SiCl2S4 skeleton.

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    Volume 2017, Issue 1 (January 3, 2017), Pages 186–191 

    Silylene-Induced Reduction of [Mn2(CO)10]: Formation of a Five-Coordinate Silicon(IV) Complex with an O-Bound [(OC)4Mn=Mn(CO)4]2– Ligand

    Authors:

    Johannes A. Baus, Jordi Poater, F. Matthias Bickelhaupt and Reinhold Tacke

    DOI: 10.1002/ejic.201600913

    Abstract:

    Based on a new silylene-induced reduction of [Mn2(CO)10], a five-coordinate silicon(IV) complex was synthesized, which is formally built up by an anionic [(OC)4Mn=Mn(CO)4]2– and a cationic {[iPrNC(NiPr2)NiPr]2Si}2+ fragment, which are connected by a nearly linear Si–O–C moiety. The Si–O and the C–O bond of this Si–O–C moiety display partial double-bond character.

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    Dalton Transactions 2017, Advance Article

    DOI: 10.1039/C6DT03264H,  Received 18 Aug 2016, Accepted 27 Sep 2016
    First published online 07 Oct 2016

    DOI: 10.1039/c6dt03264h   read more ...

    Neutral six-coordinate bis(dithiocarbamato)-silicon(IV) complexes with an SiCl2S4 skeleton

    Dr. Johannes A. Baus and Prof. Dr. Reinhold Tacke

    Graphical abstract: Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton


    Abstract

    Treatment of SiCl4 with lithium dithiocarbamates of the formula type Li[R2NCS2] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(IV) complexes [Ph2NCS2]2SiCl2 (3) and [iPr2NCS2]2SiCl2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(IV) complexes with an SiCl2S4 skeleton.

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    Prof. Dr. Reinhold Tacke
    Institut für Anorganische Chemie
    Am Hubland
    97074 Würzburg

    Tel.: +49 931 31-85250
    Fax: +49 931 31-84609
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