Hartmut Schubert

University of Tuebingen, Tübingen, Baden-Württemberg, Germany

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Publications (18)79.63 Total impact

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    ABSTRACT: The linker-bridged distannene [(2,6-Mes2)C6H3Sn]2C12H8 (1) featuring an acenaphthene linker and the sterically demanding terphenyl substituent Ar(Me) (= C6H3-2,6-Mes2; Mes = C6H2-2,4,6-Me3) was prepared and characterized by single-crystal analysis, NMR spectroscopy, as well as elemental analysis. Furthermore, the reactivity of distannene 1 and previously reported distannenes 2 and 3, bearing either a naphthalene or a 9,9-dimethylxanthene backbone and the terphenyl substituent Ar(Me), as well as bis(stannylene) 4, featuring a 9,9-dimethylxanthene backbone and the terphenyl substituent Ar(iPr) (= C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3), toward terminal alkynes at ambient temperature was investigated, leading to the formal [2 + 2] cycloaddition products 5-9. The reactions of distannene 1 with trimethylsilylacetylene and phenylacetylene, the reaction of distannene 2 with trimethylsilyl-acetylene, as well as the reaction of bis(stannylene) 4 with phenylacetylene show reversibility, while distannenes 2 and 3 react irreversibly with phenylacetylene at room temperature. A van't Hoff analysis of variable-temperature (1)H NMR spectra of the cycloadduct of the reaction of distannene 1 with trimethylsilylacetylene afforded a dissociation enthalpy (ΔHdiss) of 71.6 kJ·mol(-1), which is in surprisingly good agreement with the results of accompanying DFT calculations (ΔHdiss = 70.9 kJ·mol(-1)).
    Inorganic Chemistry 06/2015; DOI:10.1021/acs.inorgchem.5b00896 · 4.79 Impact Factor
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    ABSTRACT: Wir berichten über die Synthese und Charakterisierung eines Allyl-SnII-Komplexes, der eine η3-Koordination in Lösung und im Festkörper aufweist. Zwei Beispiele für die Reaktivität des Allylderivates werden vorgestellt: Die Reaktion mit terminalen Alkinen ergibt tricyclische Verbindungen, während die Umsetzung mit Benzonitril über eine C-H-Aktivierung zu einem 16 Atome umfassenden Ringsystem führt.
    Angewandte Chemie 03/2015; 127(18). DOI:10.1002/ange.201500386
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    ABSTRACT: We herein report the synthesis and characterization of a terphenyl-substituted Sn(II) allyl compound featuring an η(3) coordination mode in solution and in the solid state. Two examples for the interesting reactivity of the allyl Sn(II) molecule are presented: Reactions with terminal alkynes result in the formation of tricyclic compounds by CC bond formation and the dimerization of two Sn moieties whereas the reaction with benzonitrile leads to a sixteen-membered ring system through CH activation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Angewandte Chemie International Edition in English 03/2015; 54(18). DOI:10.1002/anie.201500386 · 13.45 Impact Factor
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    ABSTRACT: The coordination chemistry of cyclic stannylene-based intramolecular Lewis pairs is presented. The P→Sn adducts were treated with [Ni(COD)2 ] and [Pd(PCy3 )2 ] (COD=1,5-cyclooctadiene, PCy3 =tricyclohexylphosphine). In the isolated coordination compounds the stannylene moiety acts either as an acceptor or a donor ligand. Examples of a dynamic switch between these two coordination modes of the PSn ligand are illustrated and the structures in the solid state together with heteronuclear NMR spectroscopic findings are discussed. In the case of a Ni(0) complex, (119) Sn Mössbauer spectroscopy of the uncoordinated and coordinated phosphastannirane ligand is presented. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Chemistry - A European Journal 02/2015; 21(12). DOI:10.1002/chem.201406486 · 5.70 Impact Factor
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    ABSTRACT: NHC adducts of the stannylene Trip2 Sn (Trip=2,4,6-triisopropylphenyl) were reacted with zero-valent Ni, Pd, and Pt precursor complexes to cleanly yield the respective metal complexes featuring a three-membered ring moiety Sn-Sn-M along with carbene transfer onto the metal and complete substitution of the starting ligands. Thus the easily accessible NHC adducts to stannylenes are shown to be valuable precursors for transition-metal complexes with an unexpected SnSn bond. The complexes have been studied by X-ray diffraction and NMR spectroscopy as well as DFT calculations. The compounds featuring the structural motif of a distannametallacycle comprised of a [(NHC)2 M(0) ] fragment and Sn2 Trip4 represent rare higher congeners of the well-known olefin complexes. DFT calculations indicate the presence of a π-type Sn-Sn interaction in these first examples for acyclic distannenes symmetrically coordinating to a zero-valent transition metal. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Angewandte Chemie International Edition in English 02/2015; 54(13). DOI:10.1002/anie.201411025 · 13.45 Impact Factor
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    ABSTRACT: Bei der Umsetzung des Stannylen-NHC-Addukts Trip2Sn(NHC) (Trip=2,4,6-Triisopropylphenyl) mit Komplexverbindungen von nullwertigen Elementen der Nickeltriade erhält man Komplexe mit dreigliedrigem Sn-Sn-M-Ring unter Übertragung des Carbens auf das Metall. Die Eignung der Stannylen-Carben-Addukte als leicht zugängliche Vorstufen für Übergangsmetallkomplexe mit unerwarteter Zinn-Zinn-Bindung wird illustriert. Die erhaltenen Komplexverbindungen wurden mit Einkristall-Röntgenbeugung, NMR-Spektroskopie und DFT-Rechnungen untersucht. Die Verbindungen mit dem Strukturmotiv eines aus einem [(NHC)2M0]-Fragments und dem Distannen Sn2Trip4 zusammengesetzten Distannametallarings sind seltene Beispiele für höhere Gruppe-14-Homologe der bekannten Olefinkomplexe. DFT-Rechnungen sprechen für das Vorliegen einer π-artigen Sn-Sn-Wechselwirkung in diesen ersten Beispielen für acyclische, symmetrisch an ein nullwertiges Übergangsmetall koordinierenden Distannenen.
    Angewandte Chemie 02/2015; 127(13). DOI:10.1002/ange.201411025
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    ABSTRACT: Intramolecular stannylene-based Lewis pairs with phosphine Lewis bases were synthesized at the ortho position in benzene or the peri position in acenaphthene. The spectroscopic data of the Lewis pairs are discussed, and the reactivity toward unsaturated hydrocarbons and organic azides is presented.
    Organometallics 08/2013; 32(22):6785–6791. DOI:10.1021/om400736e · 4.25 Impact Factor
  • Angewandte Chemie 05/2013; 125(21). DOI:10.1002/ange.201301153
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    ABSTRACT: Bermuda triangle: The first molecule containing a cyclic three-membered SnCP ring has been synthesized and characterized. This Sn(II) P Lewis pair reacts at room temperature with alkynes and pentene to give the five-membered cyclic addition products. In the case of pentene, this reaction is reversible at room temperature. Trip=2,4,6-iPr3 C6 H2 .
    Angewandte Chemie International Edition 05/2013; 52(21). DOI:10.1002/anie.201301153 · 11.26 Impact Factor
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    ABSTRACT: N-[2-P(i-Pr)(2)-4-methylphenyl](2)(-) (PNP) pincer complexes of tin(IV) and tin(II), [(PNP)SnCl(3)] (2) and [(PNP)SnN(SiMe(3))(2)] (3), respectively, were prepared and characterized by X-ray diffraction, solution and solid state NMR spectroscopy, and (119)Sn Mössbauer spectroscopy. Furthermore, (119)Sn cross polarization magic angle spinning NMR spectroscopic data of [Sn(NMe(2))(2)](2) are reported. Compound 2 is surprisingly stable toward air, but attempts to substitute chloride ligands caused decomposition.
    Inorganic Chemistry 04/2012; 51(10):5787-94. DOI:10.1021/ic300324s · 4.79 Impact Factor
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    ABSTRACT: A much improved synthesis for the carbagerma-closo-dodecaborate anion [GeCB10H11](-) is described in the form of [Bu3NH][GeCB10H11] (1). In reactions with transition metal electrophiles, three transition metal complexes {[Bu3NH][(C6H6)Ru(Cl)(2)(GeCB10H11)] (2), [Bu3NH][Cp*Ir(Cl)(GeCB10H11)(2)] (3) and [Me3NH][(PPh3)(2)Ir(CO)(GeCB10H11)(2)] (4)} with metal-germanium bonds were synthesized. The carbagermaborate anion, in the form of the salt [Et3NH][GeCB10H11], and the coordination compounds 2-4 were structurally characterized by single-crystal X-ray diffraction. Computations were carried out for the anions in 14 to aid NMR assignments.
    Berichte der deutschen chemischen Gesellschaft 08/2011; 2011(22-22):3349-3356. DOI:10.1002/ejic.201100310
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    ABSTRACT: This article describes the synthesis and characterization of the first silver complex with the germylene [GeB(11)H(11)](2-) and coinage metal complexes with the stannylene ligand [SnB(11)H(11)](2-). Starting materials like CuCl, AuCl(Me(2)S), and AgNO(3) were used to give mononuclear (3 and 4), dinuclear (5), hexanuclear (6), and heptanuclear (7) coordination compounds: [Et(4)N](5)[Cu(CH(3)CN)(SnB(11)H(11))(3)] (3), [Et(4)N](5)[Ag(SnB(11)H(11))(3)] (4), [Et(4)N](6)[{Au(SnB(11)H(11))(2)}(2)] (5), [Et(4)N](6)[{Ag(GeB(11)H(11))}(6)] (6), and [Et(4)N](9)[Ag(7)(SnB(11)H(11))(8)] (7). In case of the oligonuclear compounds 5-7 silver and gold aggregation was observed under formation of metal-metal bonds. Furthermore, the germa-closo-dodecaborate is found in a hitherto unknown μ(3)-bridging coordination mode connecting three silver atoms. The new compounds were characterized by single crystal X-ray diffraction and in the case of 3-6 also by NMR spectroscopy and elemental analysis.
    Inorganic Chemistry 12/2010; 42(13). DOI:10.1021/ic102118n · 4.79 Impact Factor
  • Hartmut Schubert, Lars Wesemann
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    ABSTRACT: The reaction of the tin nucleophile stanna-closo-dodecaborate [SnB11H11]2− with silver electrophiles resulted in the formation of silver−tin complexes. Depending on the respective co-ligands, a dimer, a tetramer, a polymer, and a three-dimensional network structure were characterized. With bipyridine and phenanthroline, dimeric complexes exhibiting very short Ag−Ag interatomic distances were isolated. With t-BuNC and pyridine, tetranuclear clusters showing tetrahedral geometry were crystallized. From the reaction of the silver salt [Et4N]8[Ag4(SnB11H11)6] with the bridging ligand 1,4-diisocyanobenzene (DIB) a linear polymeric coordination compound was formed, and a three-dimensional network structure was the product from the reaction of 1,4-diisocyanobenzene with the silver salt [Me4N][Ag(SnB11H11)]. The coordination compounds were characterized by X-ray crystal structure analysis and elemental analysis. In the case of the three-dimensional network material {[Me4N]4[Ag4(SnB11H11)4(DIB)6/2]}n (12) a single crystal to single crystal solvent exchange was found.
    Organometallics 11/2010; 29(21). DOI:10.1021/om1001556 · 4.25 Impact Factor
  • Hartmut Schubert, Fritz-Robert Küchle, Lars Wesemann
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    ABSTRACT: The tin nucleophile [SnB11H11]2– reacts with the gold cluster [Au9(PPh3)8][NO3]3 under formation of the tin–gold complex [Au8(PPh3)7(SnB11H11)] (1). In reaction with four equivalents of the heteroborate a mixed valence tetrahedral gold cluster [Au4(PPh3)4(SnB11H11)2]2– with two edge bridging tin ligands was isolated. The reaction products were characterized by elemental analysis, NMR spectroscopy and single crystal X-ray crystallography.
    Collection of Czechoslovak Chemical Communications 01/2010; 75(9). DOI:10.1135/cccc2010040 · 1.14 Impact Factor
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    ABSTRACT: The strong nucleophilic character of germa-closo-dodecaborate towards late transition metal centres is described. The synthesis and characterisation of the first germa-closo-dodecaborate complexes are presented, and the solid state structures of the germaborate transition metal complexes were determined by X-ray crystal structure analyses. The strong trans influence of the new germaborate ligand was determined by IR spectroscopy and NMR coupling constants.
    Chemistry - A European Journal 10/2009; 15(40):10613-9. DOI:10.1002/chem.200901308 · 5.70 Impact Factor
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    ABSTRACT: C22H42Ag5I7N4, orthorhombic, Pbcn (no. 60), a = 18.3099(2) Å, b = 12.1757(3) Å, c = 18.1450(3) Å, V = 4045.2 Å3, Z = 4, Rgt(F) = 0.037, wRref(F2) = 0.077, T = 173 K.
    Zeitschrift für Kristallographie 09/2008; 223(4):341. DOI:10.1524/ncrs.2008.0148 · 1.26 Impact Factor
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    01/2008; 63(8):1020-1022.
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    ABSTRACT: Stanna-closo-dodecaborate [SnB11H11]2- reacts as a nucleophile with various silver electrophiles ([Ag(PMe3)]+, [Ag(PEt3)]+, [Ag(PPh3)]+, and Ag+) to form silver-tin bonds. Aggregation of two, three, or four units of [{Ag(SnB11H11)(PR3)}n]n- (PPh3, n = 2; PEt3, n = 3; PMe3, n = 4) was found, depending on the size of the coordinating phosphine. The structures of the silver-tin clusters in the solid state were determined by single-crystal X-ray diffraction. In these phosphine silver coordination compounds, the tin ligand exhibits micro2- and micro3-coordination with the silver atoms. From the reaction with silver nitrate, an octaanionic stanna-closo-dodecaborate coordination compound, [Et4N]8[Ag4(SnB11H11)6], was isolated. In this cluster, arranged as butterfly, the stannaborate shows various coordination modes at four silver atoms. In the reported silver-tin complexes, the silver-silver interatomic distances are in a range of 2.6326(10)-3.1424(6) A. Silver-tin distances were found between 2.6416(5) and 3.1460(6) A. Analysis of the molecular orbitals calculated by means of density functional theory shows that the LUMO of the core compound without [SnB11H11]2- units is always a totally symmetric combination of (mainly) s-orbitals of Ag atoms. This core is filled with electrons of the HOMOs of the [SnB11H11]2- units and is leading, in this way, to a stable compound.
    Inorganic Chemistry 09/2007; 46(16):6775-84. DOI:10.1021/ic700464d · 4.79 Impact Factor