Untersuchungen zur Oxydation von N-Alkyl-bis-(difluorophosphor(III))-amiden

Investigations on the Oxidation of N-Alkyl-bis(difluoro-phosphorus(III))amides Oxidation of RN(PF₂)₂ by N₂O₄ in n-hexane leads to bis(difluorophosphoryl)amides, RN(POF₂)₂ (R = Me, Et), in good yields. Only one phosphorus atom is oxidized by phenylazide resulting in the formation of 1.3-diphenyl-2.4-bis(difluorophosphorus(III)-N-alkyl-amido)-2.2.4.4-tetrafluoro-diaza-λ⁵,λ⁵ diphosphetidines, [F₂P? N(R)? PF₂NPh]₂.     

Fluoraustauschreaktionen an Metalltrifluorphosphin-Komplexen. IX. Zum Reaktionsverhalten von Tetrakis(trifluorphosphin)nickel(0) gegenüber Alkyl(trimethylsilyl)aminen und -amiden

Fluorine Exchange in Trifluorophosphine Metal Complexes. IX¹. (Reactions of Tetrakis(trifluorophosphine)nickel(0) with Alkyl(trimethylsilyl)amines and Amides²) Alkylaminodifluorophosphine complexes Ni(PF₃)_4-n(PF₂NHR)_n (n = 1, 2, 3) 8–11 and Me₃SiF are obtained, if alkyl(trimethylsilyl)amines NHR(SiMe₃) (R?CH₃ and n-C₄H₉) are reacted with Ni(PF₃)₄ ( 1 ). The mechanism of these peripheric reactions is discussed by assuming a four centered type intermediate. However reactions of 1 with the lithium amides LiNR(SiMe₃) (R = CH₃, C₂H₅, n-C₄H₉, and C₆H₅) yield LiF and the difluorotrimethylsilylaminophosphine complexes Ni(PF₃)_4-n[PF₂NR(SiMe₃)]_n (n = 1, 3, 4) 12–18 .     

Pentamethylcyclopentadienyl-rhodium and -iridium complexes : XXVIII. Properties and x-ray crystal structures of [(RhC5Me5)3(H)3O]+ and [(RhC5Me5)2(H)2OAc]+ prepaerd from reactions of [RhC5Me5)2(OH)3]+ with alcohols

The triμ-hydroxo-dirhodium complexes [(RhC₅Me₅)₂(OH)₃]X (X  Cl. PF₆, BF₄) react in isopropanol to give the tri-μ-hydrido-trirhodium complexes [(RhC₅Me₅)₂(H)₃O]X (X  PF₆, BF₄, BPh₄). A combination of X-ray crystal structure determination and ¹H and ¹³CNMR spectroscopy of [RhC₅Me₅)₃-(H)₃O][PF₆] showed it to contain an equilateral triangle of rhodium, each η⁵-bonded to a C₅Me₅, capped on one sid by an oxygen and with each pair of rhodiums bridged on the other side by a hydride (RhH mean 1.7(1) Å). The molecule is quite rigid and the barrier to movement of the hydrides, ΔG3, is at least 21 kcal mol^-1 at +100°C. Reasons for this rigidity are considered. The known tetrahydride complex[(RhC₅Me₅)₄]²⁺ is obtained from [(RhC₅Me₅)₂(OH)₃]Cl in isopropanol using longer reaction times. Reaction of [RhC₅Me₅)₂(HO)₃]PF₆ with primary alcohols (RCH₂OH) gave mixtures of [(RhC₅Me₅)₂H(O₂CR)₂PF₆ and [(RhC₅Me₅)₂(H)₂(O₂CR)₂PF₆, but only the latter could be easily isolated. A single crystal X-ray structure of [(RhC₅Me₅)₂-(H)₂(O₂CMe)]PF₆ showed it to be dinuclear with two rhodiums each η⁵-binded to C₅Me₅ and bridged by two hydrides (mean RhH, 1.72(10) Å) and one acetate.     

Die Reaktion der Zweikomponentensysteme P(OR)3 − x(NR2)x (x = 0–3)/CCl4 und P4/CCl4 mit HF-Donatoren

Reaction of the Two-component Systems P(OR)_{3 ? x}(NR₂)_x (x = 0–3)/CCl₄ and P₄/CCl₄ with HF-Donators The combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF₅]^? and (RO)₂P(O)F are obtained from P(OR)₃, (Et₂N)₂P(O)F and (Et₂N)₂(EtO)PF₂ from P(OEt)(NEt₂)₂ as well as (Et₂N)₃PF₂ and [(Et₂N)₃PF]⁺ from P(NEt₂)₃. In the system R₂NH/CCl₄/Et₃N · n HF P₄ is fast oxidized forming [HPF₅]^?, R₂NH · PF₅ and (R₂N)₂P(O)F. In the case of simultaneous addition of alcohols [(RO)PF₅]^?, (RO)₃PO and (R₂N)₂P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature.     

Gemischtligandkomplexe des Rheniums. IX. Reaktionen am Nitridoliganden von [ReN(Me2PhP)(Et2dtc)2]. Synthese,Charakterisierung und Kristallstrukturen von [Re(NBCl3)(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2] und [Re(NS)Cl(Me2PhP)2(Et2dtc)]

Mixed-ligand Complexes of Rhenium. IX. Reactions on the Nitrido Ligand of [ReN(Me₂PhP)(Et₂dtc)₂]. Synthesis, Characterization, and Structures of [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] BCl₃, GaCl₃ and S₂Cl₂ react with the well-known [ReN(Me₂PhP)(Et₂dtc)₂] by attack of the nucleophilic nitrido ligand. Final products of these reactions are [Re(NBCl₃)-(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂Et₂dtc)] which have been studied by mass spectrometry, IR spectroscopy and X-ray diffraction. [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in the triclinic space group P1 , Z = 2, a = 8.151(6), b = 9.935(8), c = 18.67(1) Å; α = 94.42(4), β = 97.09(1), γ = 101.35(4)°. The coordination geometry is a distorted octahedron. The equatorial coordination sphere is occupied by one phosphorus and three sulphur atoms. The fourth sulphur atom is in trans position to the Re?N? B moiety. The almost linear Re?N? B unit has an Re?N? B angle of 170.5(3)° with a Re? N bond length of 1.704(3) Å. The analogous [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in P2₁/c with a = 8.138(3), b = 18.279(2), c = 19.880(6) Å; β = 99.81(2)°; Z = 4. Rhenium has a distorted octahedral environment. The Re? N? Ga bond is slightly bent with an angle of 154.5(4)° and a Re? N bond length of 1.695(6) Å. [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] crystallizes in the triclinic space group P1 , Z = 4, a = 9.514(2); b = 16.266(5); c = 18.388(3) Å; α = 88.75(2), β = 76.59(2), γ = 85.50(2)° with two crystallographically independent molecules in the asymmetric unit. Rhenium has a distorted octahedral environment with the chloro ligand in trans position to the almost linear thionitrosyl group. The Re?N bond lengths are 1.795(6) and 1.72(1) Å, respectively, and the N?S distances are 1.55(1) and 1.59(1) Å, respectively.     

Pentamethylcyclopentadienyl ruthenium(II) complexes of para-substituted N-(pyrid-2-ylmethylene)-phenylamine ligands: syntheses,spectral and structural studies

The reaction of [(η⁵-C₅Me₅)Ru(PPh₃)₂Cl] (1) with acetonitrile in the presence of excess NH₄PF₆ leads to the formation of the cationic ruthenium(II) complex [(η⁵-C₅Me₅)Ru(PPh₃)₂(CH₃CN)]PF₆ (2). The complex (2) reacts with a series of N,N′ donor Schiff base ligands viz. para-substituted N-(pyrid-2-ylmethylene)-phenylamines (ppa) in methanol to yield pentamethylcylopentadienyl ruthenium(II) Schiff base complexes of the formulation [(η⁵-C₅Me₅)Ru(PPh₃)(C₅H₄N-2-CHN-C₆H₄-p-X)]PF₆ [3a]PF₆–[3f]PF₆, where C₅Me₅ = pentamethylcylopentadienyl, X = H, [3a]PF₆, Me, [3b]PF₆, OMe, [3c]PF₆, NO₂, [3d]PF₆, Cl, [3e]PF₆, COOH, [3f]PF₆. The complexes were isolated as their hexafluorophosphate salts. The complexes were fully characterized on the basis of elemental analyses and NMR spectroscopy. The molecular structure of a representative complex, [(η⁵-C₅Me₅)Ru(PPh₃)(C₅H₄N-2-CHN-C₆H₄-p-Cl)]PF₆ [3e]PF₆, has been established by X-ray crystallography.     

Spectral, structural and DFT studies of platinum group metal 3,6-bis(2-pyridyl)-4-phenylpyridazine complexes and their ligand bonding modes

Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (L^ph) with [(η⁶-arene)Ru(μ-Cl)Cl]₂ (arene = C₆H₆, p-ⁱPrC₆H₄Me and C₆Me₆), [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂, (M = Rh and Ir) and [(η⁵-Cp)Ru(PPh₃)₂Cl] (Cp = C₅H₅, C₅Me₅ and C₉H₇) afford mononuclear complexes of the type [(η⁶-arene)Ru(L^ph)Cl]PF₆, [(η⁵-C₅Me₅)M(L^ph)Cl]PF₆ and [(Cp)Ru(L^ph)(PPh₃)]PF₆ with different structural motifs depending on the π-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(η⁶-C₆H₆)Ru(L^ph)Cl]PF₆1, [(η⁶-p-ⁱPrC₆H₄Me)Ru(L^ph)Cl]PF₆2, [(η⁵-C₅Me₅)Ir(L^ph)Cl]PF₆5, [(η⁵-Cp)Ru(PPh₃)(L^ph)]PF₆, (Cp = C₅H₅, 6; C₅Me₅, 7; C₉H₇, 8) show the type-A binding mode (see text), while complexes [(η⁶-C₆Me₆)Ru(L^ph)Cl]PF₆3 and [(η⁵-C₅Me₅)Rh(L^ph)Cl]PF₆4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(η⁶-C₆Me₆)Ru(μ-Cl)Cl]₂ and [(η⁵-C₅Me₅)Rh(μ-Cl)Cl]₂ complexes compared to the other starting precursor complexes. Binding modes of the ligand L^ph are determined by ¹H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.     

Gemischtligandkomplexe des Technetiums. XV. Zur Reaktion von [TcNCl2(Me2PhP)3] mit Dialkyldithiocarbamaten und N,N-Dialkylthiocarbamoylbenzamidinen

Mixed-ligand Complexes of Technetium. XV. The Reaction of [TcNCl₂(Me₂PhP)₃] with Dialkyldithiocarbamates and N,N-Dialkylthio-carbamoylbenzamidines [TcN(Cl)(Me₂PhP)₂(Et₂dtc)], [TcN(Me₂PhP)(Et₂dtc)₂], and [TcN(Et₂dtc)₂] can be prepared by stepwise ligand exchange reactions starting from dichlorotris(dimethylphenylphosphine)nitridotechnetium(V), [TcNCl₂(Me₂PhP)₃], and diethyldithiocarbamate. In contrast to this, only one intermediate, [TcN(Cl)(Me₂PhP)₂(HEt₂tcb)], could be isolated during the reaction with N,N-Diethlthiocarbamoylbenzamidine, which yields the bis chelate [TcN(HEt₂tcb)₂]. [TcN(Me₂PhP)(Et₂dtc)₂] crystallizes in the monoclinic space group P2₁/c; a = 17.369(5) Å, b = 15.024(1) Å, c = 9.906(3) Å, β = 76.47(1)º, Z = 4. The phosphine is coordinated equatorially. The multiply bonded nitrogen ligand (Tc? N(1) 1.624(3) Å) strongly labilizes the trans positioned donor atom (distance Tc? S(4) 2.826(1) Å). [TcN(HEt₂tcb)₂] crystallizes in the triclinic space group P1 with a = 9.749(4) Å, b = 11.264(4) Å, c = 12.359(4) Å, α = 75.34(2)º, β = 79.69(2)º, γ = 87.55(2)º, Z = 2. The metal is five-coordinate with the nitrido donor atom occupying the apex of a square pyramid. It's basal plane is formed by the cis-coordinated chelate ligands. The technetium is situated over the basal plane by about 0.6 Å. The Tc?N distane was found to be 1.610(5) Å.     

Characterization of [ReO(Tetramethylthiourea)4](PF6)3 in Solution: Electrochemical,NMR and Ligand Substitution Studies

The complex [ReO(Me₄tu)₄]³⁺, with Me₄tu = tetramethylthiourea, is characterized in nonaqueous media. Its structure is studied in acetonitrile solution by ¹H and ¹³C NMR and its electrochemical behavior in the same solvent is analyzed by means of cyclic voltamperometric measurements. Heteronuclear correlation and variable temperature NMR experiments suggest that the complex ion shows a similar structure in solution and in the solid state. At low temperatures (below 0°C) free rotation of the dimethylamine groups around the thiocarbonyl carbon-nitrogen bond is restricted and the dissolved complex adopts the rigid structure observed in the solid state. Cyclic voltamperometric results suggest that the redox behavior of this compound can be explained through an E_rC_iE_r mechanism (a chemical reaction coupled between two electron-transfer reactions). An initial one electron reduction of the complex from Re(V) to Re(IV) followed by an irreversible chemical reaction, leads to a new electroactive species of Re(IV)*, which is reduced to Re(III). The ability of [ReO(Me₄tu)₄](PF₆)₃ to serve as a precursor for other Re(V) complexes by ligand substitution is established, in acetone solution, with different kinds of incoming ligands: diethyldithiocarbamate (Et₂dtc), ethylenediamine (en) and pyridine (py). The previously known complexes [Re^v ₂O₃(Et₂dtc)₄], [Re^VO₂(en)₂](PF₆) and [Re^VO₂(py)₄](PF₆) are easily synthesized under mild conditions with high yields.     

Übergangsmetallphosphidokomplexe. XVII. Reaktionen von Silylphosphanderivaten mit (R3P)2PtCl2 (R = Et,Ph)

Transition Metal Phosphido Complexes. XVII. Reactions of Silylphosphine Derivatives with (R₃P)₂PtCl₂ (R ? Et, Ph) In reactions of (Et₃P)₂PtCl₂ 1a with LiP(SiMe₃)₂ at low temperatures the substitution products (Et₃P)₂Pt[P(SiMe₃)₂]Cl 2a and (Et₃P)₂Pt[P(SiMe₃)₂]₂ 3a are formed first. At ambient temperature from 3a P(SiMe₃)₃ and PEt₃ are split off yielding a mixture of the diphosphene complex (Et₃P)₂Pt[η²-(PSiMe₃)₂] 4a and the phosphido-bridged platinum(I) complex [Et₃PPtP(SiMe₃)₂]₂(Pt? Pt) 5a . Heating 2a to 80°C in solution gives the P₂-complex [(Et₃P)₂Pt]₂P₂ 6a . 4a and 6a are also obtained reacting 1a with [(Me₃Si)₂P]₂. From 1a and [Me₃Si(Me₃C)P]₂ the diphosphene complex (Et₃P)₂Pt[η²-(PCMe₃)₂] 8a is available. In the reaction of 1a with (Me₃Si)₂P? P(CMe₃)SiMe₃ the formation of the asymmetric diphosphene complex (Et₃P)₂Pt[η²-Me₃SiP?PCMe₃] 9a can be proved n.m.r. spectroscopically. Analogous reactions of (Ph₃P)₂PtCl₂ 1b with LiP(SiMe₃)₂, and with [Me₃Si(Me₃C)P]₂ are much more difficult to survey. The complexes (Ph₃P)₂Pt[η²-(PSiMe₃)₂] 4b , [(Ph₃P)₂Pt]₂P₂ 6b , and (Ph₃P)₂Pt[η²-(PCMe₃)₂] 8b are formed in n.m.r. spectroscopically detectable amounts but could not be isolated as pure compounds. N.m.r. and mass spectral data are reported.     

Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.     

Tetracyanido(difluorido)phosphates M+[PF2(CN)4]−

The systematic study of the reaction of M[PF₆] salts and Me₃SiCN led to a synthetic method for the synthesis and isolation of a series of salts containing the unprecedented [PF₂(CN)₄]^? ion in good yields. The reaction temperature, pressure, and stoichiometry were optimized. The crystal structures of M[PF₂(CN)₄] (M=[nBu₄N]⁺, Ag⁺, K⁺, Li⁺, H₅O₂⁺) were determined. X‐ray crystallography showed the exclusive formation of the cis isomer in accord with ³¹P and ¹⁹F solution NMR spectroscopy data. Starting with the K[PF₂(CN)₄] the room temperature ionic liquid EMIm[PF₂(CN)₄] was prepared exhibiting a rather low viscosity.     

Kristallstruktur des Bis[lithium-tris(trimethylsilyl)-hydrazids] und Reaktionen mit Fluorboranen, -silanen und -phosphanen

Crystal Structure of Bis[lithium-tris(trimethylsilyl)hydrazide] and Reactions with Fluoroboranes, -silanes, and -phospanes Tris(trimethylsilyl)hydrazine reacts with n-butyllithium in n-hexane to give the lithium-derivative 1 . The reaction of 1 with SiF₄, PhSiF₃, BF₃ · OEt₂, F₂BN(SiMe₃)₂ and PF₃ leads to the substitution products 2–6 . The 1,2-diaza-3-bora-5-silacyclopentane 7 is formed by heating (Me₃Si)₂N? N(SiMe₃)(BFNSiMe₃)₂ ( 5 ) at 250°C. In the reaction of (Me₃Si)₂N? N(SiMe₃)PF₂ ( 6 ) with lithiated tert.-butyl(trimethylsilyl)amine the hydrazino-iminophosphene (Me₃Si)₂N? N = P? N(SiMe₃)(CMe₃) ( 8 ) is obtained. In the molar ratio 2:1 1 reacts with SiF₄ and BF₃ · OEt₂ to give bis[tris(trimethylsilyl)hydrazino]silane 9 and -borane 10 .     

Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12‐Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II)

The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N₄Me₂) ligand, yielding complexes of the general formula [(L‐N₄Me₂)Ru(µ‐tape)M(L‐N₄Me₂)](ClO₄)₂(PF₆)₂ with M = Fe {[ 2 ](ClO₄)₂(PF₆)₂}, Co {[ 3 ](ClO₄)₂(PF₆)₂}, and Ni {[ 4 ](ClO₄)₂(PF₆)₂}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)₂Ru(μ‐tape)PdCl₂](PF₆)₂ {[ 5 ](PF₆)₂} and [(dmbpy)₂Ru(μ‐tape)PtCl₂](PF₆)₂ {[ 6 ](PF₆)₂}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]⁴⁺ and [ 4 ]⁴⁺ were discussed on the basis of the X‐ray structures of [ 2 ](ClO₄)₄ · MeCN and [ 4 ](ClO₄)₄ · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Lithiumhydridosilylamide R2(H)SiN(Li)R′ – Darstellung,Eigenschaften und Kristallstrukturen

Lithium Hydridosilylamides R₂(H)SiN(Li)R′ – Preparation, Properties, and Crystal Structures The hydridosilylamines R₂(H)SiNHR′ ( 1 a : R = CHMe₂, R′ = SiMe₃; 1 b : R = Ph, R′ = SiMe₃; 1 c : R = CMe₃, R′ = SiMe₃; 1 d : R = R′ = CMe₃) were prepared by coammonolysis of chlorosilanes R₂(H)SiCl with Me₃SiCl ( 1 a , 1 b ) as well as by reaction of (Me₃C)₂(H)SiNHLi with Me₃SiCl ( 1 c ) and Me₃CNHLi with (Me₃C)₂(H)SiCl ( 1 d ). Treatment of 1 a–1 d with n-butyllithium in equimolar ratio in n-hexane resulted in the corresponding lithiumhydridosilylamides R₂(H)SiN(Li)R′ 2 a–2 d , stable in boiling m-xylene. The amines and amides were characterized spectroscopically, and the crystal structures of 2 b–2 d were determined. The comparison of the Si–H stretching vibrations and ²⁹Si–¹H coupling constants indicates that the hydrogen atom of the Si–H group in the amides has a high hydride character. The amides are dimeric in the solid state, forming a planar four-membered Li₂N₂ ring. Strong (Si)H … Li interactions exist in 2 c and 2 d , may be considered as quasi tricyclic dimers. The ‘‘NSiHLi rings”︁”︁ are located on the same side of the central Li₂N₂ ring. In 2 b significant interactions occurs between one lithium atom and the phenyl substituents. Furthermore all three amides show CH₃ … Li contacts.     

Diamino-di-tert-butylsilane als Bausteine cyclischer (SiN)2−, (SiNBN)2−, (SiN2Sn)- und spirocyclischer (SiN2)2Si-, (SiN2Sn)2S-Verbindungen

Diamino-di-tert-butylsilanes - Building Blocks for Cyclic (SiN)₂, (SiNBN)₂, (SiN₂Sn), and Spirocyclic (SiN₂)₂Si, (SiN₂Sn)₂S Compounds The aminochlorosilanes (Me₃C)₂SiClNHR ( 1 : R?H, 2 : R?Me) are obtained by the ammonolysis ( 1 ) respectively aminolysis ( 2 ) of di-tert-butyldichlorosilane in the n-hexane. The dilithium derivative of diamino-di-tert-butylsilane reacts with FSiMe₂R′ ( 3 : R′?Me, 4 : R′?F) in a molar ratio 1 : 2 to give the 1,3,5-trisilazanes 3 and 4 , (Me₃C)₂SiNHSiMe₂R′, in a molar ratio 1 : 1 with F₃SiN(SiMe₃)₂ to give the 1,3-diaza-2,4-disilacyclobutane 5 , (Me₃C)₂Si(NH)₂SiFN(SiMe₃)₂, and with F₂BN(SiMe₃)₂ to give the 1,3,5,7-tetraaza-2,6-dibora-4,8-disilacyclooctane 6 , [(Me₃C)₂SiNH-BN(SiMe₃)₂-NH]₂. The dilithium derivative of di-tert-butyl-bis(methylamino)silane reacts with SiF₄ with formation of the 1,3,5-trisilazane 7 , (Me₃C)₂Si(NMeSiF₃)₂, and the spirocycic compound 8 , [(Me₃C)₂Si(NMe)₂]₂Si, with SnCl₂ the cyclosilazane 9 , (Me₃C)₂SiNMe₂ is obtained. The dilithium derivative of 3 reacts with SnCl₂ to give the cyclo-1,3-diaza-2-sila-4-stannylen 10 , (Me₃C)₂Si(NSiMe₃)₂Sn. The oxidation of 10 with elemental sulfur leads to the formation of the spirocyclus 11 , [(Me₃C)₂Si(NSiMe₃)₂SnS]₂.     

Oxidative cleavage of the FeFe bond in [C5Me5Fe(CO)2]2 using ferrocinium ion: A facile route to the synthetically useful complexes [C5Me5Fe(CO)2(solvent)]+

Complexes of the type {Fp′(solvent)}⁺ PF₆^?, 3a–3d, (Fp′ = (η -C₅Me₅)Fe(CO)₂, solvent = THF, CH₃COCH₃, CH₃CN, or pyridine) are conveniently prepared by the reaction between Fp′₂ and Cp₂Fe⁺ PF₆ (Cp = η⁵-C₅H₅) in the solvent under ambient conditions. The complexes {Fp′L}⁺ PF₆^?, 3e–3g, (L = CO, PPh₃, P(OPh)₃) are readily prepared from {Fp′THF}⁺. Fp′H is formed by treatment of 3a with NaBH₄. Fp′SC(S)NMe₂ can be prepared from 3a or 3e and NaSC(S)NMe₂.     

Reactions of bis(trimethylsilyl)amine and -amide with MoOCl4

Oxo-Mo(VI) imido-chloride, [MoOCl₂(NH)(Et ₂O)] _n and nitrido-chloride, [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n have been synthesized by equimolar reactions of MoOCl₄ with HN(SiMe ₃)₂ and LiN(SiMe ₃)₂, respectively. Higher molar reactions of HN(SiMe ₃)₂ lead to imido-silylamido derivatives, [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , whereas those of LiN(SiMe ₃)₂ give silylimido bridged compounds, Mo₄O₄Cl₄(NSiMe ₃)₆ and Mo₄O₄(NSiMe ₃)₈. Elemental analyses, redox titration, magnetic moment, molecular weight, molar conductance, infrared,¹H-NMR and TG-DTG-DTA studies are reported.

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Reaktionen von Bis(trimethylsilyl)amin und -amid mit MoOCl₄

Zusammenfassung Durch equimolare Reaktionen von MoOCl₄ mit HN(SiMe ₃)₂ und LiN(SiMe ₃)₂ wurden die Oxo-Mo(VI) Imido-chloride [MoOCl₂(NH)(Et ₂O)] _n und die Nitrido-chloride [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n dargestellt. Höhermolekulare Reaktionen von HN(SiMe ₃)₂ führen zu Imido-silylamido Derivaten [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , währenddessen die von LiN(SiMe ₃)₂ silylimidoüberbrückte Verbindungen ergeben: Mo₄O₄Cl₄(NSiMe ₃)₆ und Mo₄O₄(NSiMe ₃)₈. Die Strukturen sind mit Elementaranalysen, Redoxtitrationen, Messung der magnetischen Momente, Molekulargewichten, molarer Leitfähigkeit, Infrarot,¹H-NMR und TG-DTG-DTA-Untersuchungen charakterisiert.