Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 16. Mitt.

The reaction of trimethylsilylcarbonamides with halogeno-diorganyl-boranes resp. trihalogenoboranes or organodihalogenoboranes gives monomeric resp. dimeric amidoboranes (borylcarbonamides) and derivatives of 4,8-diaza-1,5-dibora-2,6,9-trioxabicyclo[3.3.1]nonadienes. By reaction of the free acylamides with halogenoboranes in most cases the imide halides could be isolated as the only products. By reaction of the hydrochloride of bis(dimethylamino)-hydroxyborane withn-butyl-lithium followed by addition of the imide halides, the corresponding imidoylamines were formed.¹H,¹¹B, and¹⁹F-nmr spectra, mass spectra and characteristic ir group frequencies are reported.

15. Mitt.:W. Maringgele undA. Meller, Z. anorg. allg. Chem., im Druck.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekeln. VI. Amidohalogenborane

Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules. VI. Amidohalogenoboranes N-substituted halogenoacetamides react with halogenoboranes and (halogeno)-organoboranes resp. under formation of N-substituted imidohalides and (or) dimeric or (and) monomeric amidoboranes. In certain cases, carbiminoxidboranes and, as by-products, bis-(amido)boranes were isolated. By reaction of 2-trifluoracetylamino-benzonitrile with halogenoboranes and organohalogenoboranes resp. derivates of 1,3,2-diazaboranaphthaline were obtained, which decomposed on attempted sublimation at 0,001 Torr. ¹H, ¹¹B, and ¹⁹F n.m.r. spectra, mass spectra and characteristic i. r. group frequencies are reported.     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 12. Mitteilung

N-Trimethylsilylamides react with aminohalogenoboranes in nearly quantitative yield to monomeric amido(bis)aminoboranes. From the reaction of N-substituted acylamides with bis(amino)halogenoboranes and dialkoxyhalogenoboranes respectively and triethylamine corresponding amido-bis(amino)-and amido-bis(alkoxy)boranes were obtained in high yields. In certain cases equilibria between monomeric and dimeric forms are observed.¹H,¹¹R, and¹⁹F.-n.m.r. spectra, mass spectra and characteristic i.r. group frequencies are reported.

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11. Mitt.:W. Maringgele undA. Meller, Chem. Ber., eingereicht.     

Umsetzung von metall- und metalloidverbindungen mit mehrfunktionellen molekülen : XIII. Herstellung von thioamidoboranen durch SiN-spaltung

N-Trimethylsilylthioamides with the trimethylsilyl group in the N-position react with haloboranes and haloorganylboranes with elimination of the halosilane to give monomeric and dimeric thioamidoboranes, respectively. The monomeric compounds mostly exist as mixtures of cis-trans isomers. Borotrope equilibria have also been found. ¹H, ¹¹B and ¹⁹F NMR spectra, mass spectra and IR spectra are reported.     

Umsetzungen Von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen. XXVIL. Ureidoborane

Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules. XXVII. Ureidoboranes N′, N′-Diorganyl-N-organyl-N-trimethylsilylureas react with halogenodiorganylboranes to yield the N′, N′-diorganyl-N-organylureidoboranes 1–19 and 20 , which partially exists as isoureidoborane. ¹H, ¹³C, ¹¹B n.m.r. spectra, mass spectra, and i.r. group frequencies are reported.     

Umsetzungen von Tetrafluor-1,2-ethandisulfenyldichlorid mit Ketonen und Olefinen

Reactions of Tetrafluoro-1, 2-ethanedisulfenyldichloride with Ketones and Olefines The reaction of ClSCF₂CF₂SCl 1 with (CH₃)₃C? C(O)CH₃, hexene, diacetyl, cyclobutanone, and H₂C?CHC(O)CH₃ leads to the cyclic and acyclic products 2 – 6 . They are destillable liquids, which have been characterized on the basis of elemental analysis, mass spectra, ¹⁹F-, ¹³C-, and ¹H-n.m.r. spectra. The reaction mechanism will be discussed.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 7. Mitt.: Thioamidoborane

N-substituted thioamides react with bromo(organyl)boranes under formation of the corresponding thioamidoboranes and HBr. The¹¹B-NMR-spectra as well as the boiling points show, that these compounds are mostly dimeric at room temperature, resp. monomeric in the vapor-phase.¹H-,¹¹B-NMR-spectra and the mass spectra are reported.

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6. Mitt.:W. Maringgele undA. Meller ²     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 22. Mitt.: Die Reaktion von Trimethylsilylcarbonsäureamiden mit Halogen(diorganyl)boranen

Trimethylsilylacetamide and trimethylsilyltrifluoroacetamide react with halogenodiorganylboranes to monomeric or dimeric amidoboranes depending on the organyl substituents. The compounds were characterized analytically and spectroscopically (NMR:¹H,¹⁹F,¹¹B; MS; IR).

21. Mitt.:A. Meller, W. Maringgele, K. Hennemuth undU. Sicker, J. Z. anorg. allg. Chem., im Druck.     

Umsetzungen von Metall-und Metalloidverbindungen mit mehrfunktionellen Molekülen, 4. Mitt.

Alkylideniminoxy-dimethylboranes are obtained from the corresponding organic oximes and bromo-dimethylborane. Equilibria between the monomeric and dimeric form of the title compounds can be easily followed by¹H- and¹¹B-NMR-spectroscopy. Additional characterisation is given by mass spectrometry, i.r. and analytical data.

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3. Mitt.:A. Meller undW. Gerger, Mh. Chem.105, 684 (1974).     

Untersuchungen an Selen-Verbindungen. LVIII. Uber die Addukte des Selentrioxids mit Trimethylamin und Pyridin

Complexes of trimethylamine resp. pyridine with bis(trimethylsilyl)selenate decompose to yield hexamethyldisiloxane and the complexes (CH₃)₃N · SeO₃ resp. C₅H₅N · SeO₃ · IR spectra indicate that tetrameric molecular units (D · SeO₃)₄ according to the structure of selenium trioxide can be excluded. The spectra are assigned to monomeric D · SeO₃ molecules with a trigonal pyramidal NSeO₃ sceleton. They are compared with those of similar complexes. There are correlations between the complex strength and the wave numbers of the internal vibrations of the donor molecules.     

Umsetzungen von Borazinderivaten mit Bis(trimethylsilyl)-acetamid und Lithiumhexamethyldisilazan

Bis-(trimethylsilyl)acetamide (BSA) reacts with borazines [RNBX]₃, R=H,X=F; R=CH₃,X=F; R=C₆H₅,X=F and R=C₆H₅,X=Cl to the corresponding borazines,X=OSi(CH₃)₃. The¹H-NMR signal of the Si(CH)₃-groups of [C₆H₅NBOSi(CH₃)₃]₃ is at abnormally high field. With [CH₃NBCl]₃,BSA forms borazines which contain both Si(CH₃)₃O- and O?C(CH₃)=NSiR₃ groups bonded to the boron atoms. With LiN[Si(CH₃)₃]₂, [CH₃NBCl]₃ forms silylaminoboranes.¹H-NMR, mass spectrometric and analytical data are reported.     

Reaktionen von Fluorphosphoranen mit dem N,O-Bis(trimethylsilyl)-Derivat des o-Aminophenols

Reactions of Fluorophosphoranes with the N,O-Bis(trimethylsilyl) Derivative of o-Aminophenol The reaction of the N,O-bis(trimethylsilyl) derivative of o-aminophenol, 5 , with the tetrafluorophosphoranes, RPF₄, 2a–2d , (R = F, Me, Ph, and 1-adamantyl) in a 1:1 molar ratio led to monocyclic-1,3,2λ⁵-4,5-benzoxazaphospholes, C₆H₄(O)(NH)PF₂R, 6a–6d . ¹⁹F n.m.r. spectroscopic studies suggest a trigonal-bipyramidal structure with the C₆H₄(O)(NH) grouping attached to one axial and one equatorial position at five-coordinate phosphorus for these compounds. The spirophosphoranes, [C₆H₄(O)(NH)]₂PR, 8a – 8d (R = F, Me, Ph, 1-adamantyl) were obtained from the reaction of the appropriate tetrafluorophosphorane, RPF₄, 2a – 2d with 5 in a 1:2 molar ratio. The compounds 8a – 8d also result from a spontaneous scrambling reaction of 6a – 6d , with the corresponding tetrafluorophosphoranes, RPF₄ ( 2a – 2d ) as the other product. Reaction of the difluorophosphorane, Bu₃ⁿPF₂ with 5 and with N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea furnished the cyclic, fluorine-free phosphoranes, 9 and 10 , respectively. The phosphonium bromide, Bu₃ⁿPFBr, reacted with 5 in a 1:1 and a 2:1 molar ratio to produce the ionic compounds, [C₆H₄(OSiMe₃)(NHPBu₃ⁿ)]⁺Br^?, 11 , and [C₆H₄(OPBu₃ⁿ)HNPBu₃ⁿ]²⁺ 2 Br^?, 12 , respectively.     

Umsetzungen einiger Schwefel-Fluor-Verbindungen mit Verbindungen von übergangsmetallen; Darstellung und spektroskopische Untersuchung von Sulfito-Komplexen mit MnII,Mo0 und W0

Reactions of some Sulfur-Fluorine Compounds with Compounds of Transition Metals; Synthesis and Spectroscopic Investigation of Sulfito Complexes, involving Mn^II, Mo⁰, and W⁰ In the oxidative addition reactions of sulfuryl fluoride ( 1 ) and of methanesulphonic acid fluoride ( 2 ) with η²-ethylene-bis(triphenylphosphine)platinum(0) the novel ionic binuclear tetrakis(triphenylphosphine)-(μ-fluoro)-(μ-peroxo)-platinum(II)-fluorosulfonate and -methylsulfonate complexes 3 a and 3 b were formed. O,O-Sulfito-manganese(II) tricarbonyl 5 a and the binuclear μ-disulfito-dimanganese decacarbonyl complex 6 a were obtained in the reaction of disulfuryl difluoride ( 4 ) with the carbonyl metalate complex, Na⁺[Mn(CO)₅]^?. In this redox reaction several further products (e.g., CO, SO₂F₂ ( 1 ) and Mn₂(CO)₁₀) were formed and were determined quantitatively. In the presence of acetonitrile the acetonitrile-O,O-sulfito-manganese(II) tricarbonyl complex 5 b was isolated. The new binuclear complexes, bis(η⁵-cyclopentadienyl)-μ-disulfito-dimetalhexacarbonyls ( 6 b : metal = Mo⁰ and 6 c : metal = W⁰) were obtained in the reaction of 4 with the carbonyl metalates Na⁺[CpM(CO)₃]^? (M?Mo¹, W¹; Cp = cyclopentadienyl). Further products (e.g., CO, SO₂F₂ ( 1 ) and [CpM(CO)₃]₂, M?Mo, W) were formed and were determined quantitatively. The validity of the concept of hard and soft acids and bases (HSAB-concept) and of the 18-valence-electron rule (18-VE-rule) could not be confirmed in all cases. The characterization of 3a, 3b, Sb, 6b and 6c was based on their IR and NMR spectra, and in one case, on the mass spectra ( 5b ). For 3a and 3b the dynamic behaviour at room temperature in CD₂Cl₂ and CD₃OD was studied by ³¹P-NMR spectroscopy. The results are interpreted in terms of exchange processes in solution between the coordinated μ-fluoride and the solvent ligand or the uncoordinated anion. 5a and 6a and the by-products (e.g., CO and SO₂F₂ ( l )), which were formed in the redox reactions, were identified by their infrared spectra.     

Darstellung von Methyl-(trimethylsilylamino)-Fluoroalkylphosphiten und Methylamino-bis(fluoroalkylphosphiten)

Synthesis of Methyl(trimethylsilylamino) fluoroalkylphosphites and Methylamino-bis(fluoroalkylphosphites) Fluorochlorophosphites, ROPFCl I , react with heptamethyldisilazane with replacement of a trimethylsilyl group to give methyl(trimethylsilylamino)fluoroalkylphosphites, CH₃N-(PFOR)(SiMe₃) II . The introduction of a second PFOR substituent in II by further reaction with I has been possible. Thus formation of the previously unknown methylamino-bis(fluoroalkylphosphites), CH₃N(PFOR)₂ III , was observed. Compounds of type III exist in a meso form as well as in a racemic pair. ¹⁹F and ³¹P n.m.r. spectra are discussed.     

Hochdruckversuche: Umsetzungen von kohlenstoffdisulfid mit aminen,amiden und olefinen—V

Suitable tertiary amines react with CS₂, 100°C, 10⁴ atm to give N,N-disubstituted thioformamides. Salts of dialkyldithiocarbamic acids decompose at the same conditions into dialkylthioformamide and sulphur. After addition of cyclohexene, mainly N,N-dialkyldithiocarbamic acid cyclohexyl ester has been obtained. Carbon disulfide and sulphur add to olefins yielding trithiocarbonates. Dimethyl formamide reacts with CS₂ giving dimethyl thioformamide. Mechanisms are discussed with help of¹⁴CS₂ and¹⁴C-dimethyl formamide.     

Über Chalkogenolate. 163. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 2. Kristallstruktur von Dikalium-1,2-hydrazin-bis(dithioformiat)

On Chalcogenolates. 163. Reactions of Hydrazine with Carbon Disulfide. 2. Crystal Structure of Dipotassium 1,2-Hydrazine-bis (dithioformate) The title compound K₂[S₂C? NH? NH? CS₂] ( 1 ) crystallizes with Z = 4 in the orthorhombic space group Pbna with cell dimensions a = 6.635(1), b = 10.825(2), c = 12.866(2) Å. The crystal structure has been determined from single crystal X-ray data measured at ?85 °C and refined to a conventional R of 0.034 for 969 independent reflections (R_w = 0.042). The [S₂C? NH? NH? CS₂]^2? ions are linked together by hydrogen bridges N? H…?S. The K⁺ ions are surrounded by seven sulfur atoms in irregular coordination.     

Über Chalkogenolate. 113 Umsetzung von Chloramin mit Kohlenstoffdisulfid und mit Methylestern von Dithiocarbamidsäuren

On Chalcogenolates. 113. Reactions of Chloramine with Carbon Disulfide and with Methylesters of Dithiocarbamic Acids The reactions of chloramine with CS₂ and with H₂N? CS? SCH₃, CH₃? NH? CS? SCH₃, and (CH₃)₂N? CS? SCH₃ have been studied. The reaction with the methylester of dithiocarbamic acid gives the known dimethyl perthiocyanate and the reaction with the methylester of N-methyldithiocarbamic acid leads to CH₃S? CS? N(CH₃)? C(?NCH₃)? SCH₃. The latter compound has been characterized by means of electron absorption spectra, infrared spectra, nuclear magnetic resonance spectra (¹H and ¹³C), and mass spectra.     

Bildung und Eigenschaften von Acylphosphinen. II. Verbindungen aus der Reaktion von Tris(trimethylsilyl)phosphin mit Pivaloylchlorid

Syntheses and Properties of Acylphosphines. II. Compounds from the Reaction of Tris(trimethylsilyl)phosphine with Pivaloyl Chloride Tris(trimethylsilyl)phosphine reacts with pivaloyl chloride at +20°C in cyclopentane to form the enol form of pivaloylbis(trimethylsilyl)phosphine. In this compound one trimethylsilyl group is bound to phosphorus, the other to oxygen. As the n.m.r. spectra of the reaction at ?10°C in monoglyme show the thermally instable keto form with two trimethylsilyl groups bound to phosphorus is formed first and rearranges at slightly elevated temperatures. Substitution of the second trimethylsilyl group yields the enol form of dipivaloyltrimethylsilylphosphine. Tripivaloylphosphine with three acyl groups bound to phosphorus and the enol form of tert. butylpivaloyltrimethyl-silylphosphine are produced in side reactions.     

Tris[bis(trimethysilyl)amido]zinkate von Lithium und Calcium

Tris[bis(trimethylsilyl)amido]zincates of Lithium and Calcium Calcium-bis[bis(trimethylsilyl)amide] and Bis[bis(trimethylsilyl)amido]zinc yield in 1,2-dimethoxyethane quantitatively Calcium-bis{tris[bis(trimethylsilyl)- amido]zincate} · 3DME. When THF is chosen as a solvent, the two reactants and the zincate form a temperature-independent equilibrium, whereas in benzene no reaction occurs. The tris[bis(trimethylsilyl)amido]zincate anion displays characteristic ¹³C{¹H) and ²⁹Si{¹H] chemical shifts of 7 and ?8 ppm, respectively; the nature of the solvent, the cation and the complexating ligands don't influence the IR nor NMR data of the zincate anion and thus verify that [Ca(DME)₃]²⁺ and {Zn[N(SiMe_{3 2}]₃}^? appear as solvent separated ions, which is also confirmed by their insolubility in hydrocarbons.     

Zur Reaktion des 1-Lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazans mit Silicium-Fluor-Verbindungen

The Reaction of 1-Lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane with Silicon-Fluoro Compounds 1-lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane reacts with fluoroorganylsilanes RR′SiF₂ (R = F, CH₃, sec-C₄H₉; R′ = CH₃, sec-C₄H₉, C₆H₅) to give mono- and disubstituted trimethylsilylhexamethylcyclotrisilazanes and LiF. The mass-, ¹H- and ¹⁹F-n.m.r. spectra are reported.