Hartmut Schubert

Germa-closo-dodecaborate: A New Ligand in Transition-Metal Chemistry with a Strong trans Influence

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.

Homoleptic Coinage Metal Compounds of Group(IV)heteroborates

This article describes the synthesis and characterization of the first silver complex with the germylene [GeB11H11](2-) and coinage metal complexes with the stannylene ligand [SnB11H11](2-). Starting materials like CuCl, AuCl(Me2S), and AgNO3 were used to give mononuclear (3 and 4), dinuclear (5), hexanuclear (6), and heptanuclear (7) coordination compounds: [Et4N]5[Cu(CH3CN)(SnB11H11)3] (3), [Et4N]5[Ag(SnB11H11)3] (4), [Et4N]6[{Au(SnB11H11)2}2] (5), [Et4N]6[{Ag(GeB11H11)}6] (6), and [Et4N]9[Ag7(SnB11H11)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 μ3-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.

Chemistry of stannylene-based Lewis pairs: dynamic tin coordination switching between donor and acceptor character.

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.

Synthesis and characterization of N-[2-P(i-Pr)2-4-methylphenyl]2- (PNP) pincer tin(IV) and tin(II) complexes.

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.

Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity

A series of benzyl(diphenylphosphino) and o-phenyl(diphenlyphosphino) substituted germylenes and plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent and tetrylene halide. The Lewis pairs were characterized by X-ray crystallography and NMR spectroscopy. The reactivity of the tetrylenes was investigated with respect to azide addition. In the germylene case, the germaniumimide was formed as the kinetically controlled product, which rearranges upon heating to give the phosphinimide. The stannylene and plumbylene derivatives react with adamantylazide to give the azide adducts. 1-Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino-substituted germylene and plumbylene to give the cycloheteropentene molecules. The addition product between phenylacetylene and the four membered Ge-P adduct shows after addition at room temperature a 1,4-phenylmigration to give a cyclic phosphine. Alkylnitrene insertion into a Ge-C bond of the alkyne addition product of the phosphagermirane was found in reaction with adamantylazide.

η3-Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile†

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.

Nickel-Triad Complexes of a Side-on Coordinating Distannene

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.

Redox and Acid–Base Properties of Binuclear 4‐Terphenyldithiophenolate Complexes of Nickel

This work reports on the redox and acid-base properties of binuclear complexes of nickel from 1,4-terphenyldithiophenol ligands. The results provide insight into the cooperative electronic interaction between a dinickel core and its ligand. Donor/acceptor contributions flexibly adjust to stabilize different redox states at the metals, which is relevant for redox reactions like proton reduction. Proton transfer to the [S2 Ni2 ] core and Ni-H bond formation are kinetically favored over the thermodynamically favored yet unproductive proton transfer to ligand.

Low-Valent Lead Hydride and Its Extreme Low-Field 1H NMR Chemical Shift

Although hydrides of the group 14 elements are well-known as versatile starting materials in many chemical transformations, a hydride of lead in oxidation state II is so far unknown. In this work, we finally complete the jigsaw puzzle by reporting the isolation of the first low valent organolead hydride. The thermolabile dimeric organolead hydride was synthesized at low temperature and features a hydride 1H NMR signal (in solution 35.61 ppm; in the solid state 31.1 ppm) at the lowest field observed so far for a diamagnetic compound in agreement with quantum chemical predictions.

Controlling Near-Infrared Chromophore Electronic Properties through Metal–Ligand Orbital Alignment

Transition-metal complexes of radical ligands can exhibit low-energy electronic transitions in the near-infrared (NIR) spectral region. NIR band energy and intensity sensitively depend on the degree of electronic coupling of the chromophore. Using the example of open-shell complexes derived from platinum and a 1,4-terphenyldithiophenol, we present a novel approach toward spectroscopically distinct NIR dyes for which the degree of electronic coupling correlates with the relative orientation of radical ligand and metal orbitals. Ligand/metal orbital alignment is modulated by auxiliary phosphine donors and selectively results in electron localized Class II-III or delocalized Class III structures that display distinct NIR transitions at 6500 and 4000 cm-1.