bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Insertion Reactions of CH2(ã1A1) in to Some Element-Hydrogen Bonds
Authors: Koch M. , Temps F. , Wagener R. , Wagner H. Gg. 
Published: February 2015

Absolute values for the removal rates of CH2(ã1A1) by NH3, CH3NH2, CH3OH, HCl, and HF have been determined in the gas phase at low pressures and room temperature. CH2(ã1A1) was generated by pulsed laser photolysis of CH2CO. The measurements were carried out by observing the laser induced fluorescence of 1CH2 after excitation by a pulsed laser as a function of the time delay between the photolysis and analysis pulses. The overall rate constants were found to be 2.4, 2.4, 2.3, 1.6 and 0.13 · 1014 cm3/mol s, respectively.
NH2 was shown by LIF detection to be a primary product of the reaction of 1CH2 with NH3. The intersystem crossing channel of 1CH2 was investigated by monitoring the formation of CH2(X̃3B1) with laser magnetic resonance. LMR absorption intensities of 3CH2 resulting from quenching of 1CH2 in the presence and absence of the reactant R were compared under otherwise identical conditions. The branching ratios of quenching versus total removal of 1CH2, turned out to be 0.30, 0.13 and 0.98 for NH3, CH3OH, and HF, respectively.
Photophysical Properties of Hematoporphyrin and Dihematoporphyrin Ether (Ester)in Homogeneous and Microheterogeneous Environments
Authors: Köhler Gottfried , Getoff Nikola , Shopova Maria , Gantchev Tsvetan 
Published: February 2015

Abstract
Excitation wavelength effects on hematoporphyrin (HP) and hematoporphyrin derivative (HPD, Photofrin II) fluorescence spectra, quantum yields and decays were comparatively studied in homo­ geneous (at different pH and substrate concentrations) and microheterogeneous (Triton X 100 micelles and Bovine serum albumin) aqueous environments, in which the porphyrins are expected to be present in different monomer/aggregate equilibria. The observed wavelength dependences of the fluorescence yield and of short lived contributions to the total fluorescence do not correlate to the porphyrin aggregation state obtained from absorption spectra. In micro-heterogeneous environ­ ment the influence of local interactions between the porphyrin and hydrophobic sites of the cosolutes on HP and HPD photophysics is demonstrated.
On Electromagnetic Spinors and Electron Theory
Authors: Inskeep Warren H. 
Published: February 2015

Abstract
The relationship between the Dirac theory and electromagnetic spinors is extended to the case of finite mass. Certain products of the electromagnetic fields give rise to the Dirac differential operator upon the usual subsitutions for the energy and momentum. By placing mass in the proper place for the wave mechanical approach to quantum theory, the algebra of the fields, interpreted as quantum operators, may be deduced.
Corner-Cutting Tunneling in Hydride Transfer Between NAD+ Analogues
Authors: Kreevoy Maurice M. , Lee In-Sook Han 
Published: February 2015

If hydride transfer from a donor, AjH, to an acceptor, Ai
+ , involves tunneling, phenomenological theory suggests a characteristic functional relation between rate constants and the equilibrium constant, i.e. between ln (kij, H/kij, D) and In Kij. Tunneling occurs at a heavy atom separation larger than that of the transition state (saddle point). This gives the critical configuration (point of no-return) for H-transfer a larger heavy atom separation than that for D-transfer and leads to the pattern described through a corollary of Marcus theory of atom transfer. The theory is called corner-cutting because it shortens the path which represents the reaction in multi-dimensional potential energy space. If the reactions are moderately spontaneous and the variation in structure which generates the variation in kij, H, kij, D and Kij is in the acceptor, the slope of the plot of ln (kij, H/kij, D) against ln Kij is expected to be negative; if the structure variation is in the donor it is expected to be positive. Similar results are expected for proton and hydrogen atom transfer.
This behavior has now been observed, for hydride transfer between various nitrogen heterocycles (all of which may be regarded as analogues of the enzymatic cofactor, NAD+). These reactions have kij, H/kij, D~ 5. The increase of kij, H/kij, D, with increasing Kij, reported in this paper, is particularly hard to explain without corner-cutting. The present results, therefore, support the view that some tunneling is involved in most hydrogen transfer reactions, even when no anomalies are obvious.
The Liquid Phase of Superionic Conductors. MC Simulations of Molten Silver Iodide
Authors: Margheritis C. 
Published: February 2015

MC simulations, in the NpT version, were carried out on molten Agl, on the basis of the literature interionic potentials proposed for the simulation of the superionic α-phase of solid Agl. A systematic analysis showed that none of the examined potentials can satisfactorily reproduce the experimental characteristics of the melt.
Moreover, it has been pointed out that tests of pair potentials through simulations at constant volume can be misleading.
The Determination of Spin-Rotation and Spin-Spin Interaction Constants from the Microwave Spectrum of Methane
Authors: Wolf P. , Stahl W. 
Published: February 2015

Abstract
High sensitivity and resolution of our microwave Fourier transform (MWFT) spectrometer and careful analysis of the measured transients enabled us to determine very accurate spin-rotation and spin-spin interaction constants of methane. In addition we were able to increase the accuracy of the existing centrifugal distortion constants.
On the Diabaticity of He+
2
Authors: Metropoulos A. 
Published: February 2015

Abstract
The strong diabaticity of the 2Σ+
g excited states of He+
2 has been computationally verified in the region of the well known avoided crossing between the 1 2Σ+
g and the 2 2Σ+
g adiabatic states. A large transition rate between these two states has been found, which is of the order of 1015 sec-1.
X-ray Structural Study of Ferromagnetic Vitreous 0.5 La0.7Sr0.3MnO30.5B2O3
Authors: Matsubara E. , Waseda Y. , Inomata K. , Hashimoto S. 
Published: February 2015

Abstract
The ordinary x-ray diffraction profile and the anomalous x-ray scattering profiles at Sr K-absorption edge were measured in a ferromagnetic oxide glass of 0.5La0.7Sr0.3MnO30.5B2O3. The result indicates the characteristic feature of coexistence of a highly ordered perovskite La0.7Sr0.3MnO3-like region and a random network structure consisting of BO3 triangles. It is expected that the characteristic magnetic properties of this sample are attributed to this distinctive structure.
Anomalous X-ray Scattering on Amorphous Al87Y8Ni5 and Al90Y10 Alloys
Authors: Matsubara E. , Waseda Y. , Inoue A. , Ohtera  , Masumoto T. 
Published: February 2015

Abstract
The structure of a new amorphous Al87Y8Ni5, indicating high strength and good ductility, was studied by anomalous X-ray scattering (AXS). For comparison, a binary amorphous Al90Y10 alloy was also investigated. The environmental radial distribution functions around Y and Ni as well as the ordinary RDF in the ternary alloy, and the environmental RDF around Y and the ordinary RDF in the binary alloy were determined. From the analysis of these RDFs it is found that the Y atoms are completely surrounded by Al in the binary alloy, and that some of these Al atoms are replaced by Ni atoms in the ternary alloy.
Substratum Interpretation of the Sagnac-and the Aharonov-Bohm Effect
Authors: Winterberg F. 
Published: February 2015

Abstract
It is shown that a substratum interpretation reveals a close relationship between the Sagnac- and the Aharonov-Bohm-effect. The characteristic peculiarity of the Aharonov-Bohm-effect, to produce a phase shift of the electron wave function even in the absence of any electromagnetic force fields, can be duplicated by a thought experiment for light waves in the gravitational field of a massive rotating cylinder, which demonstrates that the somewhat similar Sagnac-effect is not caused by centrifugal and Corioli’s forces, as it is sometimes claimed. In the substratum interpretation, both the Sagnac and Aharonov-Bohm effect find their explanation in a rotational motion of the substratum. If the substratum flow is irrotational, having the form of a potential vortex, these effects persist even though there are no force fields present.
Ionic Conductivity in the poly(propylene glycol)-poly(methyl methacrylate)-LiCF3SO3 System
Authors: Svantesson P. A. , Albinsson I. , Mellander B.-E. 
Published: February 2015

Abstract
The temperature dependence of the ionic conductivity in the PPG-rich part of the ternary system poly(propylene glycol)-poly(methyl methacrylate)-LiCF3SO3 has been investigated. The highest conductivity values, 3 x 10-5 (ohm cm)-1 at 31 °C and 4 × 10-4 (ohm cm)-1 at 77 C, were obtained for samples which had the properties of a pressure sensitive adhesive. The temperature dependence of the ionic conductivity could be well described by the Vogel-Tammann-Fulcher equation.
Kristallstruktur von SbCl4F / Crystal Structure of SbCl4F
Authors: Minkwitz Rolf , Konikowski Detlef , Preut Hans 
Published: February 2015

Abstract
The crystal structure of SbCl4F is reported. SbCl4F crystallizes in the tetragonal space group I 4̄
with a = 1278.4(6), c = 774.1(5) pm, V = 1265(1) • 106 pm3 and Z = 8. Four SbCl4F units are linked via symmetric Sb-F-contacts forming an eight-membered heterocycles.
Polysulfonylamine, LIV [1](12-Krone-4)lithiumdimesylamid-Acetonitril (3/2): Ein Kristall mit zwei prinzipiell unterschiedlichen Konformationen des gleichen Coronanden / Polysulfonylam ines, LIV [1] (12-Crown-4)lithium Dimesylamide-Acetonitrile (3/2): A Crystal with Two Fundamentally Different Conformations of the Same Coronand
Authors: Blaschette Armand , Nagel Karl-Heinz , Jones Peter G. 
Published: February 2015

Abstract
[Li(12-crown-4){N(S02CH3)2}] is obtained from equimolar amounts of lithium dimesylamide and 12-crown-4 in methanol and crystallizes from acetonitrile as a 3/2 solvate. The crystallographic data of the latter at -130 °C are: monoclinic, space group P 2/n, a = 1053.4(3), b = 904.3(3), c = 2791.2(8) pm, β = 95.66(3)°, V = 2.646 nm3, Z = 6, Dx = 1.441 Mgm-3. Apart from CH3CN molecules residing in lattice cavities, the structure consists of two crystallographically independent [Li(12-crown-4){N(S02CH3)2}] ion pairs A and B in the ratio 2:1. In B, the Li and N atoms lie on a crystallographic twofold axis. In both ion pairs, Li is hexacoordinated by the four crown oxygen atoms O(C) and by one oxygen O(S) from each sulfonyl group of the anionic ligand. The coordination geometry of Li in A closely resembles that of CuII in the known structure of [Cu(12-crown-4)Cl2] and can be pictured as a distorted octahedron, where two cis sites are occupied by the O(S) atoms and the remaining vertices by the four oxygens of the macrocycle, which displays a [4 8] conformation. The lithium atom, the two O(S) and two O(C) atoms are arranged in an approximately square-planar pattern with L i-O (S) 203.6 and 205.1, Li-O(C) 206.9 and 219.1 pm, trans angles of 173.7 and 174.8°, and cis angles in the range 87.1 -93.6°. The angle between the remaining two Li -O(C) bonds with distances 214.7 and 221.5 pm is only 146.5° compared with 180° in an ideal octahedron. In ion pair B, the coronand assumes a [3 3 3 3] conformation close to C4 symmetry, as observ­ ed e. g. in the known structures of [Li(12-crown-4)NCS] with a square-pyramidal 0 4N-coordination and [Ca(12-crown-4)(H20)4]Cl2 · 4 H2O with a square-antiprismatic 0 8-geometry. The coordination polyhedron in B can be viewed as an incomplete cube in which two vertices related by a face diagonal are unoccupied. Important bond lengths and angles in B are: L i-O(S) 216.8, L i-O(C) 214.0 and 228.7pm; O(S) -L i-O (S) 82.0, O(C) -L i-O(C) 75.7/76.3 for adjacent and 120.4/121.9° for opposite ring oxygens.
Cycloadditionen, XXI [1]. 2-Methyl-2,3-butadiensäure-arylester; Synthese und thermische Reaktivität / Cycloadditions, XXI [1] Aryl 2-methyl-2,3-butadienoates; Synthesis and Thermal Reactivity
Authors: Himbert Gerhard , Fink Dieter , Stürm Martina 
Published: February 2015

Abstract
The substituted phenyl, 1-naphthyl or the 9-anthrylmethyl esters of the 2-methyl-(or 2-phenyl)-2,3-alkadienoic acids (see 4 a -g , 9 a -d and 12a,b) are synthesized by condensation of the allenic acids 2 a -d with the substituted phenols 3 a -g , with 1-naphthol (8) or with 9-anthrylmethanol (11) in the presence of dicyclohexyl carbodiimide (DCC) and a catalytic amount of 4-dimethylaminopyridine (DMAP). An alternative route is the reaction of the acid chloride la with the phenols 3 a -c (see formation of 4 a -c) in the presence of triethylamine. All these compounds (except 12a) undergo the intramolecular Diels-Alder (IMDA)-reaction to form the tricycles 6 a -g , 10 a-d and 13. The enol ether 6a is hydrolized during chromatography to give the tricyclic ketone 7. The influence of the geminal methyl group on the rate of the IMDA-reaction is investigated.
9-Anthryl-and (2,4,6-cycloheptatrien-1-on-2-yl)-2-methyl-2,3-butadienoate (15, 17), formed by reaction of 2-methyl-2,3-butadienoyl chloride (1a) with 9-anthrone (14) and 2-tropolone (16) isomerise spontaneously to the IMDA-products 19 and 18.
Übergangsmetallkomplexe mit Schwefelliganden, C*. Unerwartet einfache Bildung von Diazen-Komplexen und ein neuer Typ von Diastereomerie: [µ-N2H2{Fe(PPr3)('S4')}2] und analoge Komplexe mit [FeS]-Zentren. ( 'S4'2-= 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, C*. Unexpectedly Facile Formation of Diazene Complexes and a New Type of Diastereomerism: [µ-N2H2{Fe(PPr3)('S4')}2] and Analogous Complexes with [FeS]-Centers. ('S4'2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))
Authors: Sellmann Dieter , Friedrich Helge , Knoch Falk , Moll Matthias 
Published: February 2015

Abstract
Single pot reactions of FeCl2∙4H2O with the tetradentate thioether-thiol 'S4-H2' = 1,2-bis(2-mercaptophenylthio)ethane, phosphines such as PEt3, PPr3 or PBu3, and a ca. 40-fold excess of N2H4∙H2O yield, in the presence of air, diazene complexes of the general formula [µ-N2H2{Fe(PR3)('S4')}2]. In contrast to previous syntheses of diazene complexes, the yields can excel 80%, and the syntheses can be carried out on a 10 g scale.
[µ-N2H2{Fe(PPr3)('S4')}2], 1 and [µ-N2H2{Fe(PEt3)('buS4')}2], 2 were characterized by X-ray structure analysis. 2 contains 'buS4'2−= 1,2-bis(3,5-ditertiarybutyl-2-mercaptophenylthio)-ethane(2-), which is the tertiary-butyl derivative of 'S4'2−. 1 and 2 contain trans-HN=NH which bridges enantiomeric [Fe(PPr3)('S4')] or [Fe(PEt3)('buS4')] fragments. HN=NH is stabilized by 4c - 6 e− - π bonds, strong tricentric N − H∙∙∙(S)2 bridges, and steric shielding. NMR studies show that centrosymmetric 1 isomerizes in solution at temperatures around 0 °C in order to give a diastereomerie diazene complex which is also centrosymmetric. The diastereomerism is traced back to bridging the chiral [Fe(PPr3)('S4')] fragments by trans-HN=NH in a different way. The two different bridging modes are verified by X-ray structure analyses of analogous ruthenium complexes. Because this new type of diastereomerism is basically caused by a different position only of the N − H∙∙∙(S)2 bridges, it is termed hydrogen bridge diastereomerism. A mechanism for the isomerization is suggested. 1 exhibits three anodic waves in the cyclovoltammogram. The second wave indicates formation of the dication [1]2+, which is a redox isomer of the diprotonated (and as yet hypothetical) dinitrogen complex [µ-N2{Fe(PPr3)('S4')}2]. The significance of [1]2+ and of its Lewis basic thiolate donors with respect to electrochemical reduction of molecular dinitrogen under mild conditions is discussed.
1.3-Dimethyl-1,3-diaza-2-R-5,6-benzo-2λ3-phosphorinan-4-one (R = F, Me2N, 2-Methylpiperidino, MeC(: 0 )N H -) als Liganden in Übergangsmetallkomplexen; Synthese und Struktur von Dichloro-Platin(II)- und Tetracarbonyl-Metall(O)- Koordinationsverbindungen (Metall = Cr, Mo und W) / 1.3-Dimethyl-1,3-diaza-2-R-5,6-benzo-2λ3-phosphorinan-4-ones (R = F, Me2N, 2-Methylpiperidino, MeC(: 0 )NH-) as Ligands in Transition-Metal Complexes; Synthesis and Structure of Dichloro-Platinum(II)- and Tetracarbonyl-Metal(0) Coordination Compounds (Metal = Cr, Mo and W)
Authors: Plinta Hans-Jürgen , Neda Ion , Schmutzler Reinhard 
Published: February 2015

Abstract
1,3-Dimethyl-1,3-diaza-2-fluoro-5,6-benzo-1,3,2-phosphorinane-4-one (1) reacted with (COD)PtCl2 (COD = 1,5-cyclooctadiene) or K2PtCl4 to give the cis-dichloro-platinum(II) complex (2). The reactions of 1 with the tetracarbonyl norbornadiene derivatives of Cr, Mo and W furnished the complexes 3 - 6 . In the case of the chromium and tungsten complexes the trans-isomers 3 and 6 were formed, due to a cis-trans-isomerization. Room temperature and low temperature 31P NMR spectra of a mixture of 5 and 6 show no significant temperature dependence of the cis-trans equilibrium. The reaction of 1 with the pentacarbonyl tetrahydrofuran derivative of W led to the product 7. The spirophosphoranes 8 and 9 were obtained in low yields. The analogous reactions of 10, 15 and 20 with (COD)PtCl2 and the tetracarbonyl norbornadiene derivatives of Cr and Mo furnished the coordination compounds 11-14, 16-18, 21 and 23. In the case of all chromium complexes only the trans-isomers 11,16 and 21 were formed, whereas in the case of molybdenum cis-trans-isomer mixtures 12 and 13, as well as 17 and 18 were obtained. An attempt to obtain the cis-isomer of the molybdenum complex 22 failed. In the case of platinum the expected cis-complexes 14 and 23 were formed, while the attempted synthesis of 19 was unsuccessful. All these results are interpreted in terms of both steric and electronic factors. The ligands 1, 10, 15 and 20 coordinate via phosphorus. The validity of the concept of hard and soft acids and bases (HSAB) was confirmed. The characterization of 2 - 7 , 11-14, 16-18, 21 and 23 rests, especially, on their 1H, 13C and 31P NMR spectra, and their mass and infrared spectra. 31P - 31P coupling constants 2J(PP) for the cis-coordinated complexes 4, 5 and 14 involving two equivalent phosphorus ligands are also reported.
On the Chemistry of Resiniferonol, II [1] Preparation and Bioactivities of 15,16-Dihydrosimplexin and Methods for its Tritium Labeling
Authors: Schäfer T. , Sorg B. , Karalai C. , Hecker E. 
Published: February 2015

Abstract
Excoecaria factor O 1 -the daphnane type polyfunctional diterpene ester 5 β-hydroxy-6 α,7 α-epoxyresiniferonol-9,13,14-orto-(2,4,6-decatrienoate) -may be obtained in reason­ able amounts from the latex of Excoecaria oppositifolia from South East Asia. O 1 was partially hydrogenated with H2-Pd/C to yield, by saturation of the three double bonds in the orthoester, and of ⊿15,16 in the diterpene moiety, the new 15,16-dihydro derivative of simplexin. The latter is the well known daphnane prototype of polyfunctional diterpene esters occurring in Euphorbiaceae and Thymelaeaceae. 15,16-Dihydrosimplexin (DHS) showed pro­nounced irritant and tumor promoting activities. By analogous hydrogenation of O1 with a mixture of 1H2/3H2 a selectively labeled [3H]DHS was obtained that exhibited a particularly high specific activity of 30 Ci/mmole. Thus it is considered most appropriate for use to study the toxicokinetics and -dynamics of daphnane type diterpene esters. To device an alternative of 3H-labeling of DHS or simplexin (SIM) in position 20 of the diterpene moiety DHS-5-benzoate was oxidized by pyridinium chlorochromate. The resultant 20-aldehyde was reduced by sodium borohydride to reconstitute DHS-5-benzoate and, after deprotection, DHS. This route appears appropriate to prepare similarly [20-3H]DHS as well as [20-3H]SIM using sodium [3H]borohydride.
Derivate des Hydrazins als Liganden in Vanadium(III)-, -(IV)- und -(V)-Komplexen. Darstellung und Charakterisierung von [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O / Substituted Hydrazines as Ligands in Vanadium(III), -(IV) and -(V) Complexes. Synthesis and Characterization of [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O
Authors: Sundheim Angelika , Theers Christiane , Mattes Rainer 
Published: February 2015

The reaction of [VO(dipic)(H2O)2]·2H2O with benzoylhydrazine, thiobenzoylhydrazine and O-methylcarbazate yields [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)·2H2O (1), [V0(dipic)(NHNHCO2Me)] (2), [VO(dipic)(NH2NHCO2Me)] (3) and [VO(dipic)(NHNHCSPh)] (4). 1 is probably formed in solution by redox disproportionation. The reactions giving 2,3 and 4 also involve redox processes with atmospheric oxygen as oxidant and the respective hydrazine as reductant. [VO('ONO')(NHNHCOPh)]·H2O (5) was formed using aqua-oxo-salicylaldehyde-L-alaninato-vanadium(IV) as precursor. The structures of 1,2,3 and 5 have been determined by single crystal X-ray crystallography.
The cation of 1 has a seven-coordinated vanadium(III) center with the two H2O molecules at the apices of a pentagonal bipyramide, the anion contains the doubly deprotonated hydrazido( 2-) ligand NHNCOPh2- as N,O-chelate. 2 and 3 have very similar structures, but differ in the oxidation state of the vanadium atom and in the degree of deprotonation of the hydrazine. In 3 neutral NH2NHCOOMe and in 2 the single deprotonated hydrazido(l -) ligand NHNHCOOMe- are bound as N,O-chelates, with the O-donor in rrans-position to the VO group. The remaining coordination sites are occupied by the ONO-donating dinegative dipic ligand. 5, where dipic is replaced by the three-dentate salicylaldehyde-benzoyl-hydrazone, has a very similar structure to 2. 4 with a VO3N2S coordination sphere is the first vanadiun (V) complex containing the N,S-donating hydrazido(l-) ligand NHNHCSPh-. The following parameters are characteristic for the bonding of the NHNHR- and NHNR2- ligands in 1,2 and 5: V-N 189 ± 1 pm, N-N 134 ± 1 pm and V-N-N 122 ± 2°.
Lithium-zinkate mit heteroleptischem Triorganylzinkat-Anion / Lithium Zincates with Heteroleptic Triorganylzincate Anion
Authors: Westerhausen Matthias , Rademacher Bernd , Schwarz Wolfgang , Henkel Sonja 
Published: February 2015

Abstract
Bis[bis(trimethylsilyl)methyl]-as well as bis(2,2,4,4,6,6-hexa-methyl-2,4,6-trisila-cyclo-hexyl)zinc react with methyl lithium or phenyl lithium in the pres­ ence of the tridentate l,3,5-trimethyl-l,3,5-triazinane (TMTA) to yield zincates of the type LiZnR2R'·2TMTA. The compounds are colorless and insoluble in aliphatic or aromatic hydrocarbons. These zincates exist in solution as well as in the crystalline state as separated ions, as confirmed for lithium-methyl-bis(2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl)-zincate · 2TMTA by X-ray diffraction (P1̄; a -1139,5(3); b = 1482,4(4); c = 1528,6(5) pm; α = 95,33(2); β = 100,13(2); γ = 106,91(2)°; Z = 2). The lithium cation is six-coordinated by two TMTA ligands in a distorted anti-prismatic complex. The zinc atom displays a trigonal planar coordination with Zn-C bond lengths of 207 pm to the 2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl ligands and of 202 pm to the methyl group. One trisila-cyc/o-hexyl substi­ tuent exists in the chair, the other one in the twist conformation. The reaction of lithium bis(trimethylsilyl)amide with bis(trimethylsilylmethyl)zinc yields the benzene soluble lithium-bis(trimethylsilyl)amino-bis(trimethylsilylmethyl)zincate TMTA. The molecular structure was confirmed by X-ray diffraction (P212121; a -1024,8(3); b = 1775,4(7), c = 1918,2(8) pm; Z = 4). The bridging bis(trimethylsilyl)amino ligand displays long Zn-N and Li-N distances of 213 and 208 pm, respectively, due to the steric inter-ligand repulsion. During the reaction of lithium bis(trimethylsilyl)amide with bis[bis(trimethylsilyl)methyl]-zinc no zincate formations observed. The decomposition products lithium bis(trimethylsilyl)-methanide and the heteroleptic bis(trimethylsilyl)amino-bis(trimethylsilyl)methylzinc were detected.