Dianionic Tris[oxalato(2—)]silicate and Tris[oxalato(2—)]germanate Complexes: Synthesis,Properties, and Structural Characterization in the Solid State and in Solution

Reaction of tetramethoxysilane with three molar equivalents of oxalic acid and two molar equivalents of 1‐(2‐hydroxyethyl)‐pyrrolidine or 1‐(2‐hydroxyethyl)piperidine in tetrahydrofuran yielded the λ⁶Si‐silicates 1‐(2‐hydroxyethyl)pyrrolidinium tris[oxalato(2—)]silicate ( 4 ) and 1‐(2‐hydroxyethyl)piperidinium tris[oxalato(2—)]silicate ( 5 ). The related germanium compounds 1‐(2‐hydroxyethyl)piperidinium tris[oxalato(2—)]germanate ( 6 ) and triethylammonium tris[oxalato(2—)]germanate ( 7 ) were synthesized analogously, starting from tetramethoxygermane and using three molar equivalents of oxalic acid and two molar equivalents of 1‐(2‐hydroxyethyl)piperidine or triethylamine. Compounds 4 — 7 were characterized by elemental analyses (C, H, N), single‐crystal X‐ray diffraction, solid‐state VACP/MAS NMR spectroscopy (²⁹Si), and solution NMR spectroscopy (¹H, ¹³C, ²⁹Si). The structural characterization was complemented by computational studies of the tris[oxalato(2—)]silicate dianion and the tris[oxalato(2—)]germanate dianion. In addition, the stability of compounds 4 — 7 in aqueous solution was studied by ¹³C NMR spectroscopy.     

Über Tris[(trialkylphosphan)gold(I)]oxonium-tetrafluoroborate und Tris[(triphenylphosphan)gold(I)]sulfonium-tetrafluoroborat

On Tris[(trialkylphosphine)gold(I)]oxonium Tetrafluoroborates and Tris[(triphenylphosphine)gold(I)]sulfonium Tetrafluoroborate [Et₃PAu]⁺BF, obtained from Et₃PAuCl and AgBF₄ in tetrahydrofuran, reacts with KOH (molar ratio 3:1) to give the oxonium salt [(Et₃P)Au]₃O⁺BF ( 1 ). The homologous [^t(Bu₃P)Au]₃O⁺BF ( 2 ) is generated similarly from ^tBu₃PAuCl and Ag₂O in the presence of NaBF₄ in THF. The composition and identity of these two first tris[(tri alkyl phosphine)gold(I)]oxonium salts have been confirmed by analytical and spectroscopic data. The compounds are useful aurating agents. From the corresponding triphenylphosphine complex and (Me₃Si)₂S quantitative yields of the sulfonium salt [(Ph₃P)Au]₃S⁺BF ( 3 ) are obtained. Its crystal structure features monomeric cations, and in these small Au? S? Au angles indicate significant metal-metal bonding.     

Tris(dialkylamino)benzylphosphoniumbromide – Phosphoniumsalze mit drei nahezu planar konfigurierten N‐Atomen

Tris(dialkylamino)benzylphosphonium Bromides – Phosphonium Salts with three N Atoms configurated nearly planar Tris(dialkylamino)benzylphosphonium bromides [(R₂N)₃PCH₂C₆H₅]⁺Br^– (R: Me, Et, n‐Pr, n‐Bu) have been obtained by the reaction of the corresponding tris(dialkylamino)phosphines with benzylbromide in good yields. The compounds crystallize as colorless solids from acetonitrile or methylene chloride after addition of diethylether. The corresponding tris(dialkylamino)‐benzylphosphonium tribromides have been prepared by treating of the simple bromides with equimolar quantities of elemental bromine. The orange‐red precipitates have been recrystallized from the same solvents by addition of diethylether. In all compounds investigated the crystal structure analyses showing three N atoms with a nearly planar configuration.     

Zum Reaktionsverhalten der Tris(dialkylthiophosphinyl)phosphane – Die Kristallstruktur von [Ag{O[P(S)Me2]2}2] [AsF6]

Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me₂]₂}₂][AsF₆] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO₂)_m [AsF₆]_n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me₂]₂}₂][AsF₆], which is also formed by the reaction of Ag[AsF₆] with O[P(S)Me₂]₂. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively.     

Vanadium-Komplexe mit dreizähnigen diaciden Liganden. Die Kristallstrukturen von Bis[acetylacetonthiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehydthiobenzoylhydrazonato(2-)]vanadium(V) und Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanolvanadium(V)

Vanadium Complexes with Tridentate Diacidic Ligands. The Crystal Structures of Bis[acetylacetonato-thiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehyd-thiobenzoylhydrazonato(2-)]vanadium(V), and Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanol Vanadium(V) By template reactions of bis(acetylacetonato)oxovanadium(IV) and bis(salicylaldehydato)oxo-vanadium(IV), respectively, with benzoylhydrazine, thiobenzoylhydrazine, and 2-aminophenol the vanadium(IV) complexes V(LLL)₂ of tridentate azomethine ligands LLL were synthesized. The complexes were characterized by EPR spectroscopy and by absorption spectroscopy. From the complex V(LLL)₂ ( 1 ), in which LLL is acetyl-aceton-thiobenzoydrazonate(2-), the crystal structure analysis was solved. The vanadium atom in 1 is coordinated trigonal-prismatically by two N, 0 and S atoms. Furthermore, the 0x0 vanadium(V) complexes[VO(LLL)(OCH,)] (6) with LLL = salicylaldehyd-thio-benzoylhydrazonato(2-) and [VO(LLL)(OCH₃)· -CH₃OH] (7) with LLL = salicylaldehydbenzoylhydrazonato(2-) were identified by X-ray diffraction and by IR spectroscopy in the reaction products. Crystallographic data for 1, 6 , and 7 see ?Inhaltsübersicht”?.     

Synthese und Kristallstruktur der Molybdännitrido‐Komplexe [MoNCl3(MeCN)]4 und [MoNCl2(bipy)]4

Syntheses and Crystal Structures of the Nitrido Complexes [MoNCl₃(MeCN)]₄ and [MoNCl₂(bipy)]₄ [MoNCl₃(MeCN)]₄ ( 1 ) is obtained by the reaction of MoCl₄(MeCN)₂ with Me₃SiN₃ in CH₂Cl₂ as a sparingly soluble and water sensitive red compound. It crystallizes as 1 · 3 CH₂Cl₂ in the triclinic space group P 1 with a = 889.7(1), b = 1004.8(1), c = 1270.4(2) pm; α = 71.69(1)°; β = 73.63(1)°; γ = 86.32(1)°, and Z = 1. It forms centrosymmetric tetranuclear complexes, in which the Mo atoms are connected by asymmetric and linear nitrido bridges with distances Mo–N of 167.5 and 214.3 pm. The acetonitrile molecules are coordinated with a long bond length Mo–N of 241 pm in trans position to the Mo–N triple bond. The reaction of 1 with 2,2′‐bipyridine in CH₂Cl₂/THF yields the tetranuclear molybdenum(V) complex [MoNCl₂(bipy)]₄ ( 2 ) as main product. It crystallizes in the tetragonal space group P4₂/n with a = 1637.5(2), c = 1018.3(2) pm, and Z = 2. In the tetranuclear complexes with the symmetry S₄ linear and asymmetric nitrido bridges connect the Mo atoms to form an almost planar eight membered Mo–N ring with distances Mo–N of 173 and 203 pm. The bipyridine molecules coordinate as chelates in cis and trans position to the Mo–N triple bond. In this case the trans influence causes different Mo–N distances of 219 and 232 pm.     

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.     

Bromthionitren-tetrabromo-wolfram, [WBr4(NSBr)]2

Bromothionitrene-tetrabromo-tungsten, [WBr₄(NSBr)]₂ [WBr₄(NSBr)]₂ is prepared by the reaction of the corresponding chlorothionitrene complex [WCl₄(NSCl)]₂ with excess trimethylsilylbromide. Unpure [WCl₄(NSBr)]₂ was also prepared. According to the i.r. spectra the bromothionitrene complexes are similar to the chlorothionitrene complex [WCl₄(NSCl)]₂, which was characterized earlier by X-ray methods. [MoCl₄(NSCl)]₂ reacts with Me₃SiBr forming MoNBr₃.     

Tris(trimethylsilyl)silylamin und seine lithiierten und silylierten Derivate — Kristallstruktur des dimeren Lithium-trimethylsilyl-[tris(trimethylsilyl)silyl]amids

Tris(trimethylsilyl)silylamine and the lithiated and silylated Derivatives — X-Ray Structure of the dimeric Lithium Trimethylsilyl-[tris(trimethylsilyl)silyl]amide The ammonolysis of the chlor, brom or trifluormethanesulfonyl tris(trimethylsilyl)silane yields the colorless tris(trimethylsilyl)silylamine, destillable at 51°C and 0.02 Torr. The subsequent lithiation, reaction with chlor trimethylsilane and repeated lithiation lead to the formation of lithium tris(trimethylsilyl)silylamide, trimethylsilyl-[tris(trimethylsilyl)silyl]amine and finally lithium trimethylsilyl-[tris(trimethylsilyl)silyl]amide, which crystallizes in the monoclinic space group P2₁/n with a = 1 386.7(2); b = 2 040.2(3); c = 1 609.6(2) pm; β = 96.95(1)° and Z = 4 dimeric molecules. The cyclic Li₂N₂ moiety with Li? N bond distances displays a short transannular Li …? Li contact of 229 pm. The dimeric molecule shows nearly C₂-symmetry, so that one lithium atom forms agostic bonds to both the trimethylsilyl groups, the other one to the tris(trimethylsilyl)silyl substituents. However, the ⁷Li{¹H}-NMR spectrum displays a high field shifted singlet at —1.71 ppm. The lithiation of trimethylsilyl-[tris(trimethylsilyl)silyl]amine leads to a high field shift of the ²⁹Si{¹H} resonance of about 12 ppm for the Me₃SiN group, whereas the parameters of the tris(trimethylsilyl)silyl ligand remain nearly unaffected.     

Atom-Economic Synthesis of Tris[2-(organylthio)ethyl]phosphine Oxides from Phosphine and Vinyl Sulfides

Abstract

Phosphine, generated from elemental phosphorus in the system KOH-toluene-H₂O, reacts with vinyl sulfides under free radical conditions (AIBN, dioxane, 65–70°C, atmospheric pressure) to form regiospecifically tris[2-(organylthio)ethyl]phosphines, which are readily oxidized in air to corresponding tris[2-(organylthio)ethyl]phosphine oxides.     

Complex Formation of PdII Ion with the Tripodal Ligand Tris[2-(dimethylamino)ethyl]amine

The complex formation of Pd^II with tris[2-(dimethylamino)ethyl]amine (N(CH₂CH₂N(CH₃)₂)₃, Me₆tren) was investigated at 25° and ionic strength I = 1, using UV/VIS, potentiometric, and NMR measurements. Chloride, bromide, and thiocyanate were used as auxiliary ligands. The stability constant of [Pd(Me₆tren)]²⁺ in various ionic media was obtained: log β([Pd(Me₆tren)] = 30.5 (I = 1(NaCl)) and 30.8 (I = 1(NaBr)), as well as the formation constants of the mixed complexes [Pd(HMe₆tren)X]²⁺ from [Pd(HMe₆tren)(H₂O)]³⁺:log K = 3.50 = Cl^?) and 3.64 (X^? = Br^?) and [Pd(Me₆tren)X]⁺ from [Pd(Me₆tren)(H₂O)]²⁺: log K = 2.6 (X^? = Cl^?), 2.8(Br^?) and 5.57 (SCN^?) at I = 1 (NaClO₃). The above data, as well as the NMR measurements do not provide any evidence for the penta-coordination of Pd^II, proposed in some papers.     

Darstellung und Charakterisierung von Chrom(V)- und Mangan(V)- nitridophthalocyaninen(1-) und -(2-): [MNPc(1-)]+; und [MNPc(2-)] (M=Cr,Mn)

Preparation and Characterization of Chromium of Chromium(V)- and Manganese(V)- nitridophthalocyanines(1-) and -(2-): [MNPc(1-)]⁺ and [MNPc(2-)] (M=Cr, Mn) Nitridophthalocyaninatochromium(V), [CrNPc(2-)], is prepared by oxidation of [Cr(OH)₂PC(2-)] with chlorine in the presence of excess ammonia as a paramagnetic (μ_eff = 1,99 B.M.), Microcrystalline blue powder. Through chemically very stable it reacts as well as the isostructural nitridophthalocyaninatomanganese(V) with bromine or concentrated nitric acid giving ring- oxidized darkblue nitridophthalocyaninatomental(poly)bromides or -nitrates, [MNPc(1-)]X (M=Cr, Mn; X=Br_y, NO₃; y≈?2). The nitrido-metal stretching vibration (ν(N?M)) is independent of the oxidation state of the Pc-ligands at ca. 1017 cm^?1 for the chromium and at ca. 1055 cm^?1 for the manganesenitridophthalocyanines. ν(N?Mn) is resonance Raman (r.r.) enhanced, ν(N?Cr) not. The characteristic differences in the u.v. -vis., f.i.r./m.i.r. and r.r. spectra of [MNPc(2-)] and [MNPc(1-)⁺ and the influence of aggregation of phthalocyanine-radicals are discussed.     

Synthesen und Charakterisierungen der ersten Tris‐ und Tetrakis(trifluormethyl)palladate(II) und ‐platinate(II), [M(CF3)3(PPh3)]— und [M(CF3)4]2— (M = Pd,Pt)

Syntheses and Characterizations of the First Tris and Tetrakis(trifluoromethyl) Palladates(II) and Platinates(II), [M(CF₃)₃(PPh₃)]^— and [M(CF₃)₄]^2— (M = Pd, Pt) Tris(trifluoromethyl)(triphenylphosphino)palladate(II) and platinate(II), [M(CF₃)₃PPh₃]^—, and the tetrakis(trifluoromethyl)metallates, [M(CF₃)₄]^2— (M = Pd, Pt), are prepared from the reactions of [MCl₂(PPh₃)₂] and Me₃SiCF₃ / [Me₄N]F or [I(CF₃)₂]^— salts in good yields. [Me₄N][M(CF₃)₃(PPh₃)] crystallize isotypically in the orthorhombic space group Pnma (no. 62) with Z = 4. The NMR spectra of the new compounds are described.     

Darstellung und Struktur von Tris[2,4,6-tris(trifluormethyl)thiophenolato]indium(III)-diethyletherat

Preparation and Structure of Tris[2,4,6-tris(trifluormethyl)thiophenolato]indium (III) Etherate Reaction of sodium [2,4,6-tris(trifluoromethyl)thiophenolate and InCl₃ in the molar ratio of 1:3 in diethylether forms tris 2,4,6-tris(trifluoromethyl)thiophenolato]indium(III) etherate 1 in 92% yield. 1 was also obtained by reaction of CpIn (Cp = C₅H₅) and C₆H₂(CF₃)₃SH. The structure of 1 is discussed.     

[Sm(NO3)3(TPTZ)(H2O)]·2H2O [TPTZ is 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine]

The title compound, aqua­tris­(nitrato)[2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine]samarium dihydrate, [Sm(NO₃)₃­(C₁₈H₁₂N₆)­(H₂O)]·­2H₂O, was prepared from Sm(NO₃)₃·6H₂O and 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine. The metal atom is ten‐coordinate being bonded to the terdentate TPTZ ligand, three bidentate nitrates and a water mol­ecule.     

Darstellung und spektroskopische Charakterisierung der reinen Bindungsisomeren [ReX5(NCS)]2− und [ReX5(SCN)]2−, X = Cl,Br

Preparation and Spectroscopic Characterization of the Pure Bondisomers [ReX₅(NCS)]^2? and [ReX₅(SCN)]^2?, X = Cl, Br The treatment of (TBA)₂[ReBr₆] with NaSCN in acetone or of (TBA)₂[ReCl₅I] with AgSCN in CH₂Cl₂ yields mixtures of the bondisomers [ReBr₅(NCS)]^2?/[ReBr₅(SCN)]^2? or [ReCl₅(NCS)]^2?/[ReCl₅(SCN)]^2?, which are isolated as pure compounds by ion exchange chromatography on DEAE-Cellulose. The i.r. and Raman spectra are assigned according to local symmetry C_4v. The bondisomers are significantly distinguished by the frequencies of inner ligand vibrations: ν_CN(S) > ν_CN(N), ν_CS(N) > ν_CS(S), δ_NCS > δ_SCN. The electronic absorption spectra measured at 10 K exhibit in the region 6000 to 16000 cm^?1 all intraconfigurational transitions (t) splitted into Kramers dubletts by lowered symmetry (C_4v) and spin orbit coupling. The O? O transitions are deduced from vibrational fine structure. The charge transfer spectra of the bondisomers in the UV/VIS region are similar to those of the corresponding hexahalorhenates(IV).     

Kaliumpolysulfide: [K(THF)]2S6 und [K2(THF)]S9

Potassiumpolysulfides: [K(THF)]₂S₆ and [K₂(THF)]S₉ The polysulfide [K₂(THF)]S₉ is accessible from reaction of S₈ with [KSPPh₂(BH₃)]. Degradation reaction of S₈ with [KPPh₂(BH₃)] results in [K(THF)]₂S₆. X‐ray quality crystals of [K(THF)]₂S₆ (orthorhombic, Pbca) and of [K₂(THF)]S₉ (orthorhombic, Pbcm) are obtained each from THF / diethyl ether solution at ambient temperature. According to the result of the X‐ray structural analysis, [K(THF)]₂S₆ and [K₂(THF)]S₉ contain a S₆‐ and S₉‐zigzag chain. The conformation of both polysulfide anions is all‐transoid.     

Solvothermal Synthesis and Characterization of the New Iron Thioantimonates(III) [Fe(C6H18N4)]FeSbS4 and [Fe(C4H13N3)2]Fe2Sb4S10 Containing FeII and FeIII and Protein‐Analogous [2FeIII‐2S]2+ Clusters

The two new compounds [Fe(tren)]FeSbS₄ ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)₂]Fe₂Sb₄S₁₀ ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe³⁺ is part of a [2Fe^III‐2S] cluster which is often found in ferredoxines. In addition, Fe²⁺ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe²⁺ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe²⁺ ion is isolated. In both compounds the primary SbS₃ units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS₄ was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step.     

2-[2-(2,3-Dihydrobenzimidazolylidene)]- and 2-[2-(2,3-Dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones

The reaction of 2-aminocarbonyl-5,5-dimethyl-1,3-cyclohexanedione with 2,3-diaminopyridine, 1,2-phenylenediamine (and its 4-methyl, 4-nitro, 4-carboxy, and 4-benzoyl derivatives), and 3,3-diaminobenzidine gave the corresponding 2-[2-(2,3-dihydrobenzimidazolylidene)]- and 2-[2-(2,3-dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones. Their structure was confirmed by ¹H NMR spectroscopic data and X-ray analysis.     

Ir and pmr spectra of 2-aryl-4-thiazolidinones. III. Stereochemical analysis of 2-aryl-3-(2-pyridyl)-4-thiazolidinones

The long-range coupling through the sulphur atom observed in a number of 2-aryl-3-(2-pyridyl)-4-thiazolidinones suggests that the C₂ proton and one of methylene protons are in a cis 1,3 diequatorial relationship. Some additional information concerning the preferred orientations of the substituents in this system are given from Eu(fod)₃, [tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionato)]europium, induced shift data.