bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereospecific Association of C-20 Epimers of 3β-Hydroxy-16-oxo-24-nor-17-azachol-5-eno-23-nitryle
Authors: Plesnar Zofia , Malanowski Stanisław , Lotowski Zenon , Morzycki Jacek W. , Frelek Jadwiga , Wójcik Jacek 
Published: August 2018

Abstract
The cryoscopic measurements show that title compounds are strongly associated in CHCl3 solutions. The association of the 20 R epimer is distinctly less pronounced than that of the 20 S epipmer. Self-association of the 20 S epimer leads to the formation of very large com­plexes. The 20 R epimer forms associates via water molecules. The dissimilarity may be ex­plained in terms of different accessibility of the lactam carbonyl groups in the two epimers for the association. It is proposed that the association process is controlled by the configura­tion at the carbon atom C(20) and conformation around the C(20)-C(22) bond. Populations of side chain conformations of both epimers were determined by means of proton nuclear magnetic resonance. It was found for the 20 R epimer that the t and the -g rotamers are almost equally populated, and the rotamer +g is excluded. For the 20 S epimer the +g rotamer predominates over the t one, and the -g rotamer is excluded. The NMR data are fully consistent with the results of the molecular modelling studies.
1.3-Dithienium-and 1.3-Dithiolenium Salts, VI ,13C NMR Spectroscopic Investigations on 2-Substituted 1,3-Dithian-2-ylium Cations. Unusual γ-Effects
Authors: Kalinowski Hans-Otto , Stahl Ingfried 
Published: August 2018

Abstract
The 13C NMR chemical shifts of 19 2-substituted 1,3-dithian-2-ylium-tetrafluorborates 1a-1s are discussed in comparison to known analogous 1,3-dithianes and 2-lithio-1,3-dithianes. The unusual γ-effects (up to 9 ppm), which can also observed in other six-membered ring systems, are explained by the electric field effect (σ-polarisation effect). The electron density distribution can be estimated qualitatively by comparison with the 1,3-dioxan-2-ylium-and cyclohexylcations.
Chemie polyfunktioneller Moleküle, 127 PPh2-Eliminierung aus dem PP-verknüpften Phosphazen Ph2P-N=PPh2-PPh2=N-PPh2 mit [C5H5Fe(CO)(μ-CO)]2; Kristallstrukturanalyse des Phosphazen-Derivats /Chemistry of Polyfunctional Molecules, 127 PPh2 Elimination from the PP Connected Phosphazene Ph2P-N=PPh2-PPh2=N-PPh2, with [C5H5Fe(CO)(μ-CO)]2; Crystal Structure of the Phosphazene Derivative
Authors: Ellermann Jochen , Schütz Martin , Heinemann Frank W. , Moll Matthias , Bauer Walter 
Published: August 2018

Abstract
The reaction of Ph2P-N=PPh2-PPh2=N-PPh2 (Ph = C6H5, 2) with [CpFe(CO)(μ-CO)]2 (Cp = C5H5, 3) yields under elimination of a PPh2-group from 2 and cleavage of the Fe-Fe bond in 3 the monocyclic ferraphosphazene complex Cp(OC)

(4) and Ph2P-PPh2 (5). In a side reaction the P-P bond of 2 is also cleaved in a redox process to give Cp(OC)

(7). Compound 4 has been characterized by a crystal structure determination.
Synthese und Struktur eines zweikernigen Uranylkomplexes mit acyclischem, mehrzähnigem Aminoalkohol als Chelatligand: Lösungsmittelinduzierte supramolekulare Struktur/Synthesis und Structure of a Binuclear Uranyl Complex with an Acyclic, Multidentate Amino Alcohol as Chelate Ligand: Solvent Induced Supramoleculare Structure
Authors: Plass Winfried , Fries Guido 
Published: August 2018

Abstract
The pentadentate Schiff base ligand N-salicylidene-2-(bis(2-hydroxyethyl)amino)ethyl-amine (H3sabhea) reacts with uranyl dinitrate hexahydrate in methanol or ethanol to yield the binuclear uranyl complex [{UO2(Hsabhea)}2]. Depending on the solvent two crystalline modi­fications can be isolated, which were studied by single-crystal X-ray diffraction; From ethanol [{UO2(Hsabhea)}2] (1) (monoclinic space group P21/c, a = 1029.2(4) pm, b = 1342.9(6) pm, c = 1153.5(5) pm, β= 109.88(3)°, Z = 2); from methanol [{UO2(Hsabhea)}2]·2/3MeOH (2) (triclinic space group P1̄, a = 1125.9(3) pm, b= 1347.4(4) pm, c= 1632.5(6) pm, α = 91.78(3)°, β= 92.17(3)°, γ = 104.96(2)°, Z = 3). Differences between 1 and 2 are associated with the hydrogen bonding scheme involving the hydroxyethyl group as the donor, but the uranyl oxo group as acceptor for 1 and the phenolate oxygen atom as acceptor for 2. The compounds have been characterized by vibrational (IR and Raman), NMR, and UV/Vis spectroscopy. The differences in the supramolecular structure of the compounds and the related differences in their physical properties are discussed.
Structural Study of an N(4)-Substituted Thiosemicarbazone Prepared from 1-Phenyl-1,2-propanedione-2-oxime, and of a Related Nickel(II) Complex
Authors: Bermejo Elena , Castiñeiras Alfonso , West Douglas X. 
Published: August 2018

Abstract
1-Phenyl-1,2-propanedione-2-oxime reacts with 3-piperidylthiosemicarbazide and 3-hexamethyleneiminylthiosemicarbazide to give the respective 1-phenyl-1,2-propanedione-1-thiosemicarbazone-2-oximes, HPopip and HPohexim. The crystal structure of HPopip shows the oxime and thiosemicarbazone moieties in a conformation single-trans respect to carbon-carbon. A six-coordinate nickel(II) complex, [Ni(Pohexim)2], has two monoanionic (through loss of a proton from the thiosemicarbazone function) oxime-thiosemicarbazone ligands coordinated in a meridonal arrangement via the oxime nitrogen, the thiosemicarbazone imine nitrogen and the thiolato sulfur atoms. The bond distances to nickel are shorter than found for other six-coordinate complexes with monoanionic tridentate thiosemicarbazone ligands.
Metallkomplexe mit biologisch wichtigen Liganden, CXXXVII [1]. Halbsandwich-Komplexe mit N, O-Chelaten und Schiff-Basen von β-Aminosäuren/ Metal Complexes of Biologically Important Ligands, CXXXVII [1]. Halfsandwich Complexes with N, O-Chelates and Schiff Bases of β-Amino Acids
Authors: Koch Daniela , Hoffmüller Winfried , Polborn Kurt , Beck Wolfgang 
Published: August 2018

Abstract
β-Phenylalanine forms with chloro bridged complexes the chiral N, O-chelates Cp*Ir(Cl)(NH2CH(Ph)CH2CO2) and (p-cymene)Ru(Cl)(NH2CHPhCH2CO2) as mixture of two diastereoisomers. Similarly the palladium(III) and platinum(II) complexes (Et3P)(Cl)M(NH2CH(Ph)CH2CO2) (M = Pd, Pt) were obtained. Schiff base complexes (arene)(Cl)M(O2CC(R)=N-CH(R)CH(R)CH2CO2CH3) (arene = Cp*, p-cymene; M = Ir, Ru) were synthesized from the chloro-bridged compounds, 2-oxocarboxylates and β-alanine or β-phenylalanine methylester. The Cp*Ir complex with a tridendate dianionic Schiff base generated from pyruvate and β-phenylalaninate is obtained as a single isomer. Cp*Ir(Cl) forms a complex with an N, O-bidentate Schiff base ligand from glycinate and acetylacetic ethyl ester.
Notizen: Rb8AlO4Au3 ≡ Rb5AlO4 · 3RbAu – ein Aluminat-Aurid/ Rb8AlO4Au3 ≡ Rb5AlO4 · 3RbAu – an Aluminate Auride
Authors: Mudring Anja-Verena , Jansen Martin 
Published: August 2018

Abstract
Rb8AlO4Au3 (Pearson-Code oP64, P212121, a = 1043.4(1), b = 1296.7(2), c = 1320.2(2) pm, Z = 4,809 reflections with Io > 2δ(I), R1 = 0.059, wR2 = 0.151) is a further, completely new representative belonging to the group of composite alkali metal aurides. It consists of structural elem ents of alkali orthoaluminates and alkali aurides. Indeed, Rb8AlO4Au3 is thus better represented by the formula Rb5AlO4·3RbAu.
Hydroboration and Haloboration of Propyne and 1-Butyne
Authors: Bayer Michael J. , Pritzkow Hans , Siebert Walter 
Published: August 2018

Abstract
Hydroboration of propyne and 1-butyne with HBCl2 obtained from BCl3 and Me3SiH in equimolar amounts leads to 1,1-bis(dichloroboryl)alkanes 1. When BCl3 is used in excess, no 1,1-bis(dichloroboryl)alkanes 1 but E-1-dichloroborylalkene 2 besides E-1-dichloroboryl-2- chloro-alk-1-ene 3 are formed. Other by-products are tris(2-chloro-alk-1-ene-1-yl)borane 4 and bis(2-chloro-alk-1-ene-1-yl)chloroborane 5. The reaction of 3 with catechol and the formation of pyridine adducts of 4 and 5 lead to crystalline products. The composition of the products was determined by NMR spectroscopy, MS spectrometry and X-ray structure analyses of 6a, 6b, 7a and 8b.
Excited State Behavior of Uranyl Complexes with Salophen and Oxine as Chromophoric Ligands
Authors: Kunkely Horst , Vogler Arnd 
Published: August 2018

Abstract
The electronic spectra and the photochemistry of the uranyl complexes UO2 (salophen) and UO2 (oxinate)2 with H2salophen = N,N´-bis(salicylidene)-o-phenylenediamine and oxine = 8- hydroxyquinoline were studied. The excited state behavior of both complexes is determined by a low-energy salophen2- / oxinate- to U(VI) ligand-to-metal charge transfer (LMCT) state which is not luminescent but can be reactive. In the case of UO2 (oxinate)2 the photolysis leads to the formation of free oxine with ϕ = 3.6 x 10-3 at λirr = 366 nm in CHCl3. It is suggested that various redox processes with the participation of the solvent are involved in product formation. UO2 (salophen) is not light sensitive since the primary electron transfer is followed by recombination which is facilitated by the rigid UO2(salophen) structure.
5-(2-Methylphenyl)-4-pentenoic Acid from a Terrestrial Streptomycete
Authors: Mukku Venugopal J. R. V. , Maskey Rajendra P. , Monecke Peter , Grün-Wollny Iris , Laatsch Hartmut 
Published: August 2018

Abstract
From a terrestrial Streptomycete, GW 10/2517, the new 5-(2-methylphenyl)-4-pentenoic acid (1a) was isolated. The structure of 1a was proven by a detailed spectroscopic analysis and by synthesis.
N-Arylsulfonyl-benzimidazolones as Potential Hypoglycemic Agents
Authors: Ahmad Iftikhar , Hameed Shahid , Duddeck Helmut , Lenzen Sigurd , Rustenbeck Ingo , Ahmad Roshan 
Published: August 2018

Abstract
1,3-Bis(arylsulfonyl)-benzimidazolones 1a-d were synthesized by reacting benzimidazolones with arenesulfonyl chlorides in the presence of NaOH. Mono(arylsulfonyl)-benzimidazolone derivatives 5a-c were prepared from benzimidazolone by protecting one of the Natoms with a tert-butoxycarbonyl group followed by arylsulfonylation and deprotection in acidic medium. The antidiabetic activity of three compounds 1a, 1c and 5a has been determined.
Gold(I) Carboxylates and Fluorocarboxylates
Authors: Römbke Patric , Schier Annette , Schmidbaur Hubert 
Published: August 2018

Keywords
(Triphenylphosphine)gold(I) pivalate (1), and (triphenylphosphine)gold(I), [tri(p-tolyl)-phosphine]gold(I), [(4-dimethylaminophenyl)diphenylphosphine]gold(I), and (cyclohexylisocyanide) gold(I) pentafluoropropionate (2 -5) have been prepared from the corresponding gold(I) halide complexes and silver carboxylates in high yields. The products are stable to air and moisture and soluble in most common polar organic solvents. The structures of 1 and 3 have been determined. Owing to the bulk of the carboxylate substituents the molecules are monomers in the crystal. Compounds 1 - 4 undergo thermal decomposition in a narrow temperature range around 130°C, 5 is less stable and decomposes at 48° C.
Hetero-Diels-Alder Reactions of Enaminothione with Electrophilic Olefins. Synthesis of 2-Furyl Substituted 2H-Thiopyrans
Authors: Bogdanowicz-Szwed Krystyna , Budzowski Artur 
Published: August 2018

Abstract
The hetero-Diels-Alder reaction of 1-(2-furyl)-3-(dimethylamino)-2-propene-1-thione (diene) with maleic and fumaric acids, and β-nitrostyrenes yielded 3,4-dihydro-2H-thiopyran derivatives. Treatment of some of those cycloadducts with acetic acid caused elimination of dimethylamine yielding stable 2H-thiopyrans. Reaction of the diene with maleic anhydride furnished a cycloadduct which underwent spontaneous rearrangement to form an N,N-dimethylamide derivative. Cycloadditions of the diene to maleimide, N-phenylmaleimide, diethyl maleate, fumarate and butenolide, carried out in the presence of acetic anhydride,were followed by elimination of dimethylamine, afforded stable 2H-thiopyran derivatives.
Crystal Structure and Vibrational Behaviour of Tetraaqua-di(nicotinamide)M(II)-Saccharinates, with M(II) = Co, Ni, Zn
Authors: Castellano Eduardo E. , Piro Oscar E. , Parajón-Costa Beatriz S. , Baran Enrique J. 
Published: August 2018

Abstract
The crystal structures of [M(nic)2 (H2O)4](sac)2 (nic = nocotinamide; sac = saccharinate anion) with M = Co(II), Ni(II) and Zn(II), have been determined at 116 K by single-crystal X-ray diffractometry. The compounds crystallize in the triclinic space group P1̅ with Z = 1, and the M(II) cations present a slightly distorted MN2O4 octahedral environment, with equatorially coordinated water molecules and axially pyridine N-bound nicotinamide ligands. The saccharinate anions act as counteranions, and are not part of the first coordination sphere. Some comparisons with related structures have been made and the most important features of their IR spectra discussed.
Novel Nitronyl Nitroxides: Synthesis and Properties
Authors: Greve Stefan , Vill Volkmar , Friedrichsen Willy 
Published: August 2018

Abstract
The synthesis of several new nitronyl nitroxides with mesogenic groups is reported (6a, b, 11, 14a, b). Microscopic investigations revealed that in some cases (6b, 14b) highly ordered mesogenic phases are formed.
Reactivity Trends in the Reaction of Alkynes with 3-Oxo-camphorsulfonylimine
Authors: Santos A. Mafalda , Carvalho M. Fernanda N. N. , Galvão Adelino M. , Pombeiro Armando J. L. 
Published: August 2018

Abstract
The regioselective addition of deprotonated alkynes (phenyl-1-propyne, propargyl ether or tetrahydropyran-protected 3-butyn-1-ol) to the imine group was identified as a competitive process to the nucleophilic addition to the keto group of (1S)-3-oxo-camphorsulfonylimine. The selectivity of the process depends on the characteristics of the nucleophile and the reaction conditions. In the case of propargyl ether it was possible to render the imine addition the main process.
The structural characterization of compounds 1, 2, 6 by X-ray diffraction analysis show that the C2 - C3 bond becomes longer upon nucleophilic addition to the imine group of (1S)-3-oxo-camphorsulfonylimine. This trend is believed to favour the ring opening process that undergoes the formation of the spiro type compound 7.
Dinuclear Derivatives of Mn2(CO)10 with the Ligand Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane, P(C7H7)3, and their Oxidative Cleavage
Authors: Herberhold Max , Milius Wolfgang , Pfeifer Andreas 
Published: August 2018

Abstract
The photo-induced reaction of Mn2(CO)10 with the olefinic phosphane P(C7H7)3 (1; [P] if coordinated to a metal) leads stepwise to the axially substituted derivatives ax-{Mn2(CO)9[P]} (2) and ax,ax-{Mn2(CO)8[P]2} (3). Oxidative cleavage of 3 by halogens gives cis-{Mn(X)(CO)4[P]} (X = Cl (4a), Br (4b), I (4c)), whereas oxidation of 3 with NOBF4 provides a route to the salt {Mn(CO)4[P]}BF4 (5) which is also accessible by halide abstraction from 4b by AgBF4. The reactivity of the bromo complex 4b has been studied, and analogues such as cis-{Mn(R)(CO)4[P]} (R = Me (4d), Fc (4e) and N(iPr)2 (4f)) have been prepared. The displacement of a carbonyl ligand from 4b by iodide leads to mer-{Mn(I)(CO)3[P]} (6c) and by 1 to mer,trans-{Mn(Br)(CO)3[P]2} (7b). The complexes mer-{Mn(X)(CO)3[P]} (6a-c) are obtained by splitting the dimers, Mn2(CO)6(CH3CN)2- (μ −X)2 (X = Cl, Br, I), with P(C7H7)3 (1). The cation in 5 and the halogeno compounds 6a-c contain [P] (1) as a chelating four-electron ligand which uses one cyclohepta-2,4,6-trienyl substituent for π-complexation. The coordinated double bond in 6c can be displaced by phosphites P(OR)3 (R = Me, Et) to give fac-{Mn(I)(CO)3[P(C7H7)3][P(OR)3]} (8c). The structures of the new complexes 2-8 have been assigned on the basis of their carbonyl stretching absorption patterns in the IR spectra and by their NMR spectra (1H, 13C, 31P). Single-crystal X-ray structure analyses have been carried out for 3 and 6c.
Tungstenmethyl-Dimethylsilanols Cp(Oc)2(R3P)W—CH2—SiMe2OH (R = Me, Ph) – Synthesis Via Oxygenation or Hydrolysis
Authors: Hofmann Marco , Malisch Wolfgang , Hupfer Heike , Nieger Martin 
Published: August 2018

Abstract
The tungstenmethyl-dimethylsilanols Cp(OC)2(R3P)W-CH2-SiMe2OH [R = Me (6a), Ph (6b)] have been synthesized by oxofunctionalization of the tungstenmethyl-silanes Cp(OC)2(R3P)W- CH2-SiMe2H [R = Me (3a), Ph (3b)] with dimethyldioxirane. 6a has been additionally obtained by Et3N-assisted hydrolysis of the tungstenmethyl-chlorosilane Cp(OC)2(Me3P)W-CH2- SiMe2Cl (5). Compounds 6a,b are stable with respect to self-condensation, but controlled condensation of 6a with Me2Si(H)Cl in the presence of triethylamine has been realized to give the tungstenmethyl-substituted disiloxane Cp(OC)2(Me3P)W-CH2-SiMe2O-SiMe2H (7). The new compounds have been identified IR- and NMR-spectroscopically and, in the case of 3a, by X-ray analysis.
Metallkomplexe von Biologisch Wichtigen Liganden, CXLVIII [1]. Katalytische Peptidsynthese aus Glycinester miit Hilfe von Triflaten Und Cloriden der Seltenen Erden, sowie von Metall(III), (IV), (V) und (VI)-Chloriden / Metal Complexes of Biologically Important Ligands, CXLVIII [1]. Synthesis of Peptides from Glycine Ester Catalysed by Triflates and Chlorides of Metal(III, IV, V And VI) Ions
Authors: Schapp Jan , Beck Wolfgang 
Published: August 2018

Abstract
Formation of di- and triglycine ethylester which were determined by HPLC after derivatisation with dansyl chloride was observed in medium to high yields from CH2Cl2 solutions of glycine ethylester in the presence of metal triflates and metal chlorides: FeCl3 (yield 82%), AlCl3 (73%), GdCl3 (56%), La(OTf)3 (59%), Sc(OTf)3 (55%), ZrCl4 (62%), HfCl4 (60%), VOCl3 (43%), TaCl5 (29%). Esters of higher α-amino acid esters (AlaOMe, PheOMe) gave lower yields in peptide formation.
Metallkomplexe mit Biologisch Wichtigen Liganden, CIL [1]. Metallorganische η2-N,O-Lysinato-Komplexe / Metal Complexes Of Biologically Important Ligands, Cil [1]. Organometallic η2-N,O-Lysinato-Complexes
Authors: Ponikwar Walter , Beck Wolfgang 
Published: August 2018

Abstract
η2-N,O-Chelate complexes LnM[NH2CH(CO2)CH2CH2CH2CH2NH+
3 Cl-] with L-lysinate in the protected ω-ammonium form (LnM = (allyl)2Rh, (2-pyridylphenyl)2Ir, (p-cymene)(Cl)Ru, (C6Me6)(Cl)Ru, (C5Me5)(Cl)Rh, (C5Me5)(Cl)Ir) were obtained from chloro bridged complexes. A heterometallic lysinate bridged complex Cp*(Cl)IrNH2CH(CO2)(CH2)4NH2Ir(Cl)Cp* is formed with Cp*(Cl)Ir(N,O-lysinate·HCl) and [Cp*RhCl2]2.
Hydroboration of Bis(Trimethylsilyl)Ethyne. New Aspects of Hydroboration
Authors: Wrackmeyer Bernd , Tok Oleg. L. , Milius Wolfgang , Bhatti Moazzam H. , Ali Saqib 
Published: August 2018

Abstract
The hydroboration of bis(trimethylsilyl)ethyne, Me3Si-C≡C-SiMe3 1, with 9-borabicyclo [3.3.1] nonane (9-BBN) gives first the expected (Z)-alkene 5 which rearranges, without UV irradiation, after several days quantitatively into the (E)-alkene 6. Heating of 6 in the presence of a further equivalent of 1 leads, again almost quantitatively, to an allene, the 1,1,4,4-tetrakis(trimethylsilyl)-4-[9-(9- borabicyclo[3.3.1]nonyl)]buta-1,2-diene 8. Reactive structures arising from π-σ delocalisation involving the boryl group are proposed to be responsible both for the cis/trans-isomerisation and the allene formation. It is suggested that analogous structures may explain the previously observed formation of allenes 9 and 10, tin-analogues of 8. The structures of 5, 6 and 8 in solution follow from a consistent set of NMR data (1H, 11B, 13C, 29Si NMR), and the solid-state structure of 8 was confirmed by X-ray analysis.
Synthesis and Structural Characterization of the Mixed Ligand Complex [Cu(Hml)2(Phen)] · 2 H2O (H2ml = 2-Methyllactic Acid)
Authors: Carballo Rosa , Covelo Berta , Vázquez-Lópeza Ezequiel M. , Castiñeiras Alfonso , Niclós Juan 
Published: August 2018

Abstract
A new mixed-ligand complex of copper(II) with 1,10-phenanthroline and 2-methyllactate was prepared. [Cu(HmL)2(phen)] ·2H2O (where HmL = monodeprotonated 2-methyllactic acid) was characterized by elemental analysis, IR, electronic and EPR spectroscopy, magnetic measurements at room temperature, thermogravimetric analysis and X-ray diffractometry. The copper atom is in a tetragonally distorted octahedral environment and the 2-methyllactato ligand is bidentately chelating. The presence of lattice water molecules mediates the formation of a three-dimensional network.
Preparation and Crystal Structure of Hexapotassium-μ-Oxo-Hexathiodititanate(IV), K6Ti2OS6
Authors: Klepp Kurt O. , Fabian Ferdinand 
Published: August 2018

Abstract
Pale yellow crystals of the title compound were obtained by reacting an intimate mixture of K2S, K2S2O4, Ti and S at 650 °C. K6Ti2OS6 is monoclinic, mP60, s. g. P21/c. It is characterized by the formation of bitetrahedral complex anions, [S3TiOTiS3]6−, which adopt a staggered conformation. The mean Ti-S and Ti-O bond lengths are 2.242(1) and 1.836(2) Å , respectively, the Ti-O-Ti bond angle is 153.8(2)°. Two K+ ions complete the coordination of the bridging oxygen atom by the cations to a heavily distorted tetrahedral configuration. The anions are arranged in corrugated slabs running parallel to (100). The packing and crystallographic relationship to K6Co2O7 are discussed.
(Phosphine)Silver(I) Sulfonate Complexes
Authors: Römbke Patric , Schier Annette , Schmidbaur Hubert 
Published: August 2018

Abstract
Phosphine)silver(I) organosulfonate complexes of the type (R3P)AgOS(O)2R’ have been prepared in good yields from the corresponding silver sulfonates and tertiary phosphines in dichloromethane solution [R3 = Ph3, Ph2(2-Py), Me2Ph, with R’ = 4-Me-C6H4; R = Ph, R’ = Et and 2,5-Me2-C6H4]. If ethanol is present in the reaction mixture, the products contain one equivalent of ethanol. The crystal structures of (Ph3P)AgOS(O)2(C6H4-4-Me)(EtOH) (1), and (Me2PhP)AgOS(O)2(C6H4-4- Me) (5) have been determined. Complex 1 is present as a dimer in which the monomeric units feature intermolecular Ag-O donor/acceptor bonding in a four-membered ring. The coordination sphere of the silver atoms is further complemented by an ethanol molecule which is also engaged in hydrogen bonding with one of the sulfonate oxygen atoms. The solvent-free complex 5 is associated into helical chains via Ag-O coordinative bonds which provide the silver atoms with a distorted planar T-shaped coordination.
Von Fluorsilylamiden zu Element-Silylamiden und Iminosilanen
Authors: Jendras Michael , Klingebiel Uwe , Noltemeyer Mathias 
Published: August 2018

Ethyltrifluorosilane reacts with tert-butyllithium in a molar ratio 1:2 to give Et(CMe3)2SiF (1), which forms the aminosilane, Et(CMe3)2SiNH2 (2) in the reaction with NaNH2. The lithium salt of 2 and (Me3C)2SiF2 gives (Me3C)2SiF-NHSi(CMe3)2Et (3). 3 reacts with BuLi to give the lithium salt, (Me3C)2 SiF-NLi-Si(CMe3)2Et (4). tert-Butyl-(di-tert-butylfluoro)-silylaminoalanes (Me3C)2SiF-NCMe3-AlR2, R = Me (5), Et (6) are formed in the reaction of (Me3C)2SiF-NLi CMe3 (I) and ClAlR2. The lithium salt (Me3C)2SiF-NLi-Si(CMe3)2Me (III) reacts with BF3 under formation of the bis(silyl)aminodifluoroborane (Me3C)2SiF-N(BF2) Si(CMe3)2Me (7). In the reaction of I with F3SiPh rotamers of (Me3C)2SiF-NCMe3 SiF2Ph (8) are obtained.
Stannyl-silylamines are prepared in reactions of the lithium salts (Me3C)2SiF-NLiR, R = CMe3 (I), SiF(CMe3)2 (II); Si(CMe3)2Me (III) and the chlorostannanes ClSnMe3 (9,10,11) and Cl2SnPh2 (12), (Me3C)2SiF-NSnMe3-Si(CMe3)2R (9: R = F, 10: R = Me), (Me3C)2SiF-NSnMe3CMe3 (11), (Me3C)2SiF-NCMe3SnClPh2 (12). The NMR spectra of 9 and 10 prove the existence of rotamers.
The reaction of III with Me3SiOSO2 CF3 in n-hexane leads to the formation of the tris(silyl)amine 13, (Me3C)SiF-NSiMe3)2Si(CMe3)2Me. However, the analogous reaction of III and 4 with Me3SiOSO2CF3 in thf leads to the formation of the stable iminosilanes 14 and 15, (Me3C)2Si==N- Si(CMe3)R, R = Me (14), Et (15) crystal structures of 7 and 12 are presented.