Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Die ersten nicht-fluorierten Arylxenon-Kationen: Reaktionen von Xenondifluorid mit Chlorphenylbor-, -lithium-, -silicium- und -zinn-Derivaten

The First Non-fluorinated Arylxenon Cations: Reactions of Xenon Difluoride with Chlorophenylboron, -lithium, -silicon, and -tin Derivatives Tris(chlorophenyl)boranes BAr₃ (Ar = 2,6-Cl₂C₆H₃, 2,4,6-Cl₃C₆H₂) could be prepared from the reactions of ArMgI with BF₃ · O(CH₃)₂ in about 25% yield. The reactions of these boranes and of B(4-ClC₆H₄)₃ with XeF₂ in the presence of BF₃ · O(CH₃)₂ led to the formation of [XeAr][BF₄]. The compound [Xe(4-ClC₆H₄)][BF₄] was isolated in 34% yield as a colourless solid with a decomposition point of ?4 ± 2°C. The derivatives with the substituents 2,6-Cl₂C₆H₃ and 2,4,6-Cl₃C₆H₂ could only be obtained as a product mixture. Reactions of XeF₂ with Li(2,6-Cl₂C₆H₃), (CH₃)₃Si(2,6-Cl₂C₆H₃) and the hitherto unknown (CH₃)₃Sn(2,4,6-Cl₃C₆H₂) did not give evidence for the formation of an arylxenon derivative.     

Organomercury Compounds. 32. Syntheses of Fluorophenylmercurials by Decarboxylation

The organomercury compounds HgR₂ (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, m-HC₆F₄, p-HC₆F₄, or C₆F₅) and RHg(O₂CR) (R = 2-Cl,6-C₆H₃, 2,6-F₂C₆H₃ or 2,3,6-F₃C₆H₂) have been obtained in moderate – good and low yields respectively from decarboxylation reactions of the corresponding mercury(II) fluorobenzoates in boiling pyridine. By contrast, mercury(II) 2,3,4-5-tetrafluorobenzoate gave a low yield of CO₂, a trace of Hg(o-HC₆F₄)₂ and a very low yield of o-HC₆F₄Hg(O₂CC₆F₄H-o). The ¹⁹⁹Hg NMR spectra of the diorganomercurials (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, 2,4,6-F₃C₆H₂, 2,6-Cl₂C₆H₃, o-HC₆F₄, m-HC₆F₄, p-HC₆F₄ or C₆F₅) are discussed.     

Synthesen und Eigenschaften neuer Tris(fluorphenyl)antimon- und -bismut-Verbindungen. Kristallstruktur von Tris(2,6-difluorphenyl)bismut

Syntheses and Properties of Some New Tris(fluorophenyl)antimony and -bismuth Compounds. Crystal Structure of Tris(2,6-difluorophenyl)bismuth (2,6-F₂C₆H₃)₃Bi, (2,4,6-F₃C₆H₂)₃Bi, and (2,6-F₂C₆H₃)₃Sb are prepared via Grignard reactions with BiBr₃ and SbBr₃, respectively. The syntheses and properties of the new compounds and the crystal structure of (2,6-F₂C₆H₃)₃Bi are described. From the reaction of BiBr₃ with Ag(OCOC₆H₃F₂) the bismuth benzoate Bi(OCOC₆H₃F₂)₃ is formed in 83% yield. Attempts to prepare (2,6-F₂C₆H₃)₃Bi by decarboxylation of the bismuth benzoate failed.     

Synthesis, NMR spectroscopic characterisation and reactions of 2,6-difluorophenylxenon fluoride, 2,6-F2C6H3XeF

[2,6-F₂C₆H₃Xe][BF₄] is quantitatively transferred into 2,6-F₂C₆H₃XeF in reactions with [NMe₄]F. The latter has been isolated as a colourless solid which is stable in dichloromethane solution at room temperature for approximately 1 h. 2,6-F₂C₆H₃XeF readily reacts with Me₃SiX (X = Cl, Br, CN, NCO, OCOCF₃, OSO₂CF₃, C₆F₅, 2,6-F₂C₆H₃) to give compounds of general compositions 2,6-F₂C₆H₃XeX which were identified by multinuclear NMR experiments. Evidence was found for C₆H₅Xe(2,6-F₂C₆H₃) as a product of the reaction with C₆H₅SiF₃.     

2,6-Bis(methylencyclopentadienyl)-pyridin-zirconocen- und -hafnocendichlorid; Bildung und Kristallstruktur von [C5H3N-2,6-(CH2?C5H4)2Zr(Cl)(OH2)]2[ZrCl6]

2,6-Bis(methylenecyclopentadienyl)-pyridine-zirconocene and -hafnocene Dichloride; Formation and Crystal Structure of [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)[ZrCl₆]] Pyridine bridged metallocene dichlorides of type C₅H₃N-2,6-(CH₂? C₅H₄)₂MCl₂ (M = Zr ( 2 ), Hf ( 5 )) were synthesized. The presence of N → Zr interaction favours the formation of zirconocene cations. Traces of water cause the formation of the salt-like compound [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)]₂[ZrCl₆] 4 from 2 . The new compounds were characterized by ¹H n.m.r., and mass spectroscopy. The X-ray crystal structure of 4 shows discrete cations and anions which are connected by H-bridges.     

Spektroskopische und röntgenographische Untersuchungen an Dichlormethyl-Quecksilberverbindungen

Spectroscopic and X-Ray Structural Investigations on Dichloromethyl Mercury Compounds Bis(dichloromethyl)mercury, Hg(CHCl₂)₂, and mixed alkyl compounds RHgCHCl₂ (with R = CH₃, C₂H₅) have been synthesized by known methods from CH₂Cl₂, lithium butanide and HgCl₂, CH₃HgCl or C₂H₅HgCl, respectively. The ¹H-, ¹³C-NMR as well as the IR and Raman spectra of the liquid alkyls RHgCHCl₂ and the high melting Hg(CHCl₂)₂ have been measured and assigned. According to the X-ray structure determination Hg(CHCl₂)₂ crystallizes in the monoclinic space group P2₁/c with 4 non-symmetric molecules per unit cell (R = 0.046).     

Darstellung und Kristallstruktur der Kupfer(I)-chalkogenolat-2,2′-Bipyridin-Komplexe [CuS(2,4,6-iPr3C6H2)]4(Bipy)2 und [CuSe(2,4,6-iPr3C6H2)]2(Bipy)2

Synthesis and Structure of Copper(I)Chalcogenolate-2,2′-Bipyridine Complexes [CuS(2,4,6-iPr₃C₆H₂)]₄(Bipy)₂ and [CuSe(2,4,6-iPr₃C₆H₂)]₂(Bipy)₂ The oligomeric homoleptical copper(I) chalcogenolate compounds [CuS(2,4,6-iPr₃C₆H₂)]_x=4,8 and [CuSe(2,4,6-iPr₃C₆H₂)]₆ react with 2,2′-bipyridine (Bipy) to yield the tetranuclear complex [CuS(2,4,6-iPr₃C₆H₂)]₄(Bipy)₂ ( 4 ) and the dinuclear complex [CuSe(2,4,6-iPr₃C₆H₂)]₂(Bipy)₂ ( 5 ). The structures of 4 and 5 were determined by X-ray analysis. In the eight-membered Cu₄S₄ core of 4 with chair conformation the copper atoms are linked by μ₂-bridging selenolate ligands. Only two copper atoms are coordinated by 2,2′bipyridine. The corresponding copper(I) selenolate complex ( 5 ) forms a folded four-membered Cu₂Se₂ ring with μ₂-bridging selenolate ligands. The Cu? Cu distance of 2.52 Å is relatively short. In contrast to the reaction performed with 2,2′-bipyridine, addition of phenantroline to 1 respectively 2 yields a dinuclear complex [CuS(2,4,6-iPr₃C₆H₂)]₂(Phen)₂ ( 10 ). NMR spectroskopic and cryoscopic measurement of 4 show that this complex dissociates into smaller fragments in solution which undergo rapid exchange reactions. However, corresponding investigations performed on 5 indicate that the solid state structure is maintained in solution. The electrochemical behaviour of 4, 5 and 10 was studied in CH₂Cl₂ and in any case no reversible redox processes could be observed.     

Synthesis,Structure, and Lanthanide Derivatives of an Unusual Hexameric Alcohol: [2,4,6-(CF3)3C6H2CH2OH]6

Hitherto unknown 2,4,6-tris(trifluoromethyl)benzyl alcohol ( 3 ) was synthesized in 41 % yield by treatment of freshly prepared R_FLi ( 2 ) with paraformaldehyde (R_F = 2,4,6-tris(trifluoromethyl)phenyl). According to an X-ray diffraction study the crystal structure of 3 consists of S₆ symmetric cyclic hexamers [2,4,6-(CF₃)₃C₆H₂CH₂OH]₆. Deprotonation of 3 with NaN(SiMe₃)₂ in toluene afforded the unsolvated sodium alkoxide derivative R_FCH₂ONa ( 4 ). Homoleptic lanthanide alkoxides of the type Ln(OCH₂R_F)₃ (Ln = Nd ( 5 ), Sm ( 6 ), Yb ( 7 )) were made by treatment of Ln(C₅H₅)₃ with three equivalents of 3 . Similar reactions in a 1:1 molar ratio afforded the bis(cyclopentadienyl)lanthanide alkoxide derivatives (C₅H₅)₂Ln(OCH₂R_F) (Ln = Nd ( 8 ), Sm ( 9 ), Yb ( 10 )).     

Hypercoordinated diorganoantimony(III) compounds of types [2-(Me2NCH2)C6H4]2SbL and [PhCH2N(CH2C6H4)2]SbL (L = Cl,ONO2, OSO2CF3). Synthesis,structure and catalytic behaviour in the Henry reaction

The compounds [2-(Me₂NCH₂)C₆H₄]₂SbL (L = ONO₂ ( 2 ), OSO₂CF₃ ( 3 )) and [PhCH₂N(CH₂C₆H₄)₂]SbL (L = ONO₂ ( 5 ), OSO₂CF₃ ( 6 )) were prepared by reacting [2-(Me₂NCH₂)C₆H₄]₂SbCl ( 1 ) and [PhCH₂N(CH₂C₆H₄)₂]SbCl ( 4 ), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2 – 6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid-state structures for compounds 2 , 4 and 6, as well as for the hydrolysis ionic product [{2-(Me₂N⁺HCH₂)C₆H₄}{2-(Me₂NCH₂)C₆H₄}SbOH][CF₃SO₃]⁻ ( 3h ) were determined using single-crystal X-ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14-Sb-6 in 2 and 10-Sb-4 in the cation of 3h and in 4 and 6 . Compounds 1 – 6 and the starting amines PhCH₂NMe₂ and PhCH₂N(CH₂C₆H₄Br-2)₂ were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1 – 6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen.     

Triorganoantimon- und Triorganobismutderivate von Carbonsäuren fünfgliedriger Heterocyclen Kristall- und Molekülstruktur von (C6H5)3Sb(O2C-2-C4H3S)2

Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R₃M[O₂C(CH₂)ⁿ-2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) wurden durch Reaktionen von R₃Sb(OH)₂ (R = CH₃, C₆H₁₁, 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) bzw. R₃BiCO₃ mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C₄H₃X(CH₂)_nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₃ stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m^–3; V(Zelle) = 1255,6 ų; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (F_o > 3σ(F²_o)), R(ungewichtet) = 0,037]. Sb bindet drei C₆H₅-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₂ Triorganoantimony- and triorganobismuth dicarboxylates R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) have been prepared by reaction of R₃Sb(OH)₂ (R = CH₃, C₆H₁₁; 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) or R₃BiCO₃ with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph₃Sb(O₂C–2-C₄H₃S)₂ gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m^–3; V_cell = 1255.6 ų; structure determination from 3 947 independent reflexions (F_o > 3σ(F²_o)), R(unweighted) = 0.037]. Sb is bonding to three C₆H₅ groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested.     

Vibrational spectroscopic studies on the hofmann-Td-type clathrates: M(NH3)2M′(CN)4·2C6H6 (M=Mn or Cd and M′=Cd or Hg0

IR spectra of Mn(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.     

Darstellung und Eigenschaften neuer Tris(fluoraryl)borane

Preparation and Properties of New Tris(fluoroaryl)boranes B(2-FC₆H₄)₃, B(4-FC₆H₄)₃, B(2,6-F₂C₆H₃)₃ and B(C₅F₄N)₃ are prepared from the reactions of RMgX with boron trifluoride, B(OC₆F₅)₃ and B(SC₆F₅)₃ from C₆F₅XH (X = O, S) and boron trichloride. The synthetic routes and the properties of these mainly new compounds are described.     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

A first methodical approach to salts with unsymmetrical fluorophenyl(pentafluorophenyl)difluoroiodonium(V) cations [Rf(RF)IF2] (Rf=x-FC6H4, x=2, 3, 4; RF=C6F5)

A promising approach to the unknown type of [Ar′(Ar)IF₂]X salts is offered. x-FC₆H₄IF₄ (x=2, 3, 4) reacts with C₆F₅BF₂ in CH₂Cl₂ and forms [x-FC₆H₄(C₆F₅)IF₂][BF₄] salts in good yields. For [4-FC₆H₄(C₆F₅)IF₂][BF₄] the fluoro-oxidizer property is shown in reactions with weakly reducing agents like E(C₆F₅)₃ (E=P, As, Sb, Bi) and ArI (Ar=4-FC₆H₄, C₆F₅). The fluorine/aryl substitution method is also applied to the synthesis of [(4-FC₆H₄)₂IF₂][BF₄], an example with two identical aryl groups in the difluoroiodonium(V) moiety.     

Vibrational Spectroscopic Studies on the tn-Td-Type Mn(tn)Zn(CN)4_2C6H6 and the Chelated tn-Td-Type Zn(tn)Zn(CN)4_2C6H6 Clathrates

IR spectra of Mn(trimethylenediamine)Zn(CN)₄2C₆H₆ and IR and Raman spectra of Zn(trimethylenediamine)Zn(CN)₄_2C₆H₆ are reported. The spectral data suggest that the host frameworks of these compounds are similar to those of the tn-Td-type Cd(trimethylenediamine)M(CN)₄_2benzene (M = Cd or Hg) and the chelated pn-Td-type Cd(propylenediamine)Cd(CN)₄_1,2-dichloro-ethane clathrates, respectively.     

Untersuchungen an Selen-Verbindungen. LXIV. Darstellung und Eigenschaften von Säurederivaten von Phenylselen(IV) -Verbindungen (C6Hs) 2SeX2, (C6H5) 3SeX

Studies on Selenium Compounds. LXIV. Preparation and Properties of Acid Derivatives of Phenylselenium(IV) Compounds (C₆H₅) ₂SeX₂ and (C₆H₅) ₃SeX. Reactions of (C₆H₅) ₂SeBr₂ and (C₆H₅) ₃SeCl with silver salts of acids are investigated. From (C₆H₅) ₂SeBr₃ and AgY (Y = N0₃, CH₃CO₃, CF₃CO₂, 1/2 SO₄, CH₃SO₃, NCO) the compounds (C₆H₅) ₂Se(NO₃) ₂ (C₆H₅) ₂Se(CH₃CO₂) ₂, (C₆H_s) ₂Se(CF₃CO₂) ₂, (C₆H₅) ₂SeSO₄, (C₆H₅) ₂Se(CH₃SO₃) ₂ and (C₆H₅) ₂Se(NCO) ₂ are prepared. They are characterized by solubility, molecular weight and conductivity. Reaction of (C₆H₅) ₃SeCl and AgX (X = NO₃, CH₃CO₂) yields (C₆H₅) ₃SeNO₃ and (C₆H₅) ₃SeCH₃CO₂.     

The Direct Synthesis of Arylxenon Trifluoromethanesulfonates via electrophilic substitution

The reaction of xenonbis(trifluoroacetate) and trifluoromethanesulfonic acid (triflic acid) gave the new, highly reactive unsymmetrical xenon-oxo species CF₃COOXeOSO₂CF₃. Benzene derivates, containing electron withdrawing substituents such as -F, -CF₃, -Cl or -NO₂ were electrophilic attacked by this intermediate to yield arylxenon trifluoromethanesulfonates. Via this one-pot synthesis trifluoromethanesulfonates with the cations [Xe(2,4,6-F₃C₆H₂)]⁺, [Xe(2-F-5-NO₂C₆H₃)]⁺, [Xe(2-F-5-CF₃C₆H₃)]⁺ and [Xe(3,5-(CF₃)₂C₆H₃)]⁺ were prepared. All compounds were characterized by their NMR, mass, and vibrational spectra. Additionally, several new arylxenon trifluoromethanesulfonates were detected by ¹²⁹Xe-NMR spectroscopy as products of the reaction of 1,3-F₂C₆H₄ and further deactivated benzenes with xenontrifluoroacetate trifluoromethane sulfonate. Fluoro substituents in ortho position to xenon significantly increase the thermal stability of the arylxenon trifluoromethanesulfonates obtained. The molecular structure of [Xe(2,6-F₂C₆H₃)][OSO₂CF₃] was determined by single crystal diffraction methods. The arylxenon unit is weakly coordinated by one oxygen atom of the CF₃SO₃ anion. The salt crystallizes in the triclinic space group P1 , a = 880.9(3) pm, b = 1093.9(5) pm, c = 1209.8(5) pm, α = 89.04(4)°, β = 74.23(3)°, γ = 86.03(3)°, Z = 4.     

Metallorganische Verbindungen der Lanthanoide. 88. Monomere Lanthanoid(III)-amide: Synthese und Röntgenstrukturanalyse von [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)] und [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)}2(THF)]

Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C₆H₅)(SiMe₃)}₃(THF)], [Li(THF)₂(μ-Cl)₂Nd{N(C₆H₃Me₂-2,6)(SiMe₃)}₂(THF)], and [ClNd{N(C₆H₃-iso-Pr₂-2,6)(SiMe₃)} ₂(THF)] A series of lanthanide(III) amides [Ln{N(C₆H₅) · (SiMe₃)}₃(THF)_x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl₃, with LiN(C₆H₅)(SiMe₃). Treatment of NdCl₃(THF)₂ and LuCl₃(THF)₃ with the lithium salts of the bulky amides [N(C₆H₃R₂-2,6)(SiMe₃)]^? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)₂(μ-Cl)₂Nd{N(C₆H₃Me₂-2, 6)(SiMe₃)}₂(THF)] ( 11 ) and [ClLn{N(C₆H₃-iso-Pr₂-2,6)(SiMe₃)} ₂(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The ¹H- and ¹³C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed.     

Synthesen und Eigenschaften von Tetrakis(perfluoralkyl)tellur Te(Rf)4 (Rf = CF3, C2F5, C2F5, C3F7, C4F9)

Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(R_f)₄ (R_f = CF₃, C₂F₅, C₃F₇, C₄F₉) Te(CF₃)₄ is obtained from the reaction of Te(CF₃)Cl₂ with Cd(CF₃)₂ complexes as a complex with e. g. CH₃CN, DMF. It is a light and temperature sensitive hydrolysable liquid. The reaction with fluorides yields the complex anion [Te(CF₃)₄F]⁻, with fluoride ion acceptors the complex cation [Te(CF₃)₃]⁺. With traces of water an acidic solution is formed. Te(CF₃)₄ acts as a trifluoromethylation reagent. The reaction with XeF₂ gives hints for the formation of Ye(CF₃)₄F₂. Properties and NMR spectra are discussed. The much more stable complexes of Te(R_f)₄ (R_f = C₂F₅, C₃F₇, C₄F₉) are formed from the reaction of TeCl₄ with the corresponding Cd(R_f)₂ complexes.