Synthesen und Eigenschaften von Bis(perfluoralkyl)zink‐Verbindungen

Syntheses and Properties of Bis(perfluoroalkyl)zinc Compounds The conditions for the syntheses of bis(perfluoroalkyl)zinc compounds Zn(R_f)₂ · 2 D (R_f = C₂F₅, n‐C₃F₇, i‐C₃F₇, n‐C₄F₉, n‐C₆F₁₃, n‐C₇F₁₅, and n‐C₈F₁₇; D = CH₃CN, tetrahydrofurane, dimethylsulfoxide) are described. Mass spectra, thermal decompositions, ¹⁹F‐ and ¹³C‐NMR spectra 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.     

Ein Neuer Syntheseweg für Perfluororganomangan- und -rhenium-Verbindungen

A New Synthesis of Perfluoroorgano Manganese and Rhenium Compounds Pentacarbonyl perfluoroorgano manganese and rhenium compounds M(CO)₅R_f (M = Mn, Re; R_f = CF₃, C₂F₅, C₃F₇, C₄F₉, C₆F₁₃, C₆F₅) are formed as colourless solids or liquids in good yields from the reactions of M(CO)₅Br with Cd(R_f)₂ complexes in CH₂Cl₂ either in the presence of stoichiometric amounts of Ag[BF₄] or catalytic amounts of CuI. In the presence of e. g. CH₃CN the mono or disubstituted complexes M(CO)₄(CH₃CN)R_f or M(CO)₃(CH₃CN)₂R_f are formed.     

d,h-μ-Benzylalkoxophosphonato-e-μ-alkoxo-f-μ-oxo-bis[trichloroantimon(V)]-Verbindungen

d, h-μ-Benzylalkoxophosphonato-e-μ-alkoxo-f-μ-oxo-bis[trichloroantimony(V)] Compounds The binuclear antimony(V) complexes Cl₃Sb(O)[R³(R¹O)PO₂](OR²)SbCl₃ 1 – 6 with R¹ = R² = CH₃, C₂H₅ and R³ = C₆H₅CH₂, (CH₃)₃C₆H₂CH₂ in solution slowly exchanges the R² groups between the oxygen atoms of the Sb₂O₂ ring. The SbOPOSb ringsystem makes rapid pseudorotation. The isomeres are detected by nmr spectroscopy. 1 (R¹ = R² = CH₃) crystallizes in the orthorhombic space group Pnma with a = 1247.0, b = 1324.1, c = 1207.9 pm and Z = 4. 2 (R¹ = CH₃, R² = C₂H₅) and 5 (R¹ = R² = CH₃, R³ = (CH₃)₃ · C₆H₂CH₂) crystallizes triclinic in the space group P-1 with a = 984.1, b = 1026.7, c = 1079.9 pm, α = 87.93, β = 75.70, γ = 87.62° and Z = 2 and a = 1164.6, b = 1296.9, c = 1712.9 pm, α = 109.9, β = 96.3, γ = 100.2° and Z = 4 resp., with two crystallographically independent molecules in the asymmetric unit.     

Metal complexes of fluorophosphines : III. Some oxidative addition reactions of a rhodiumtrifluorophosphine complex

Some oxidative addition reactions of (CH₃)₅C₅Rh(PF₃)₂ with various iodine compounds are described. Iodine reacts with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the deep red crystalline diiodide (CH₃)₅C₅Rh(PF₃)I₂. The perfluoroalkyl iodides R_fI (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F₁₅) react with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the orange to deep red (CH₃)₅C₅Rh(PF₃)(R_f)I (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F_l5). The IR and proton and fluorine NMR spectra of these new (pentamethylcyclopentadienyl)rhodium-trifluorophosphine complexes are discussed.     

Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates

Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (R_FO)₂P(O)H in 42-89% yield, where R_F=HCF₂CH₂, H(CF₂)₂CH₂, H(CF₂)₄CH₂, CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH, CF₃(CH₃)₂C, (CF₃)₂CH₃C, CF₃CH₂CH₂, C₄F₉CH₂CH₂ and C₆F₁₃CH₂CH₂. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (R_FO)₂P(O)Cl in 49-96% yield. The chloridate (CF₃CH₂O)₂P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF₃CH₂O)₂P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF₃CH₂O)₂P(O)Br and iodidate (CF₃CH₂O)₂P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.     

Dimethyl(methansulfinyl)sulfoniumhexafluorometallate (CH3)2SS(O)CH3+MF6− (M = As,Sb) und Kristallstruktur von Methansulfinylchlorid [1]

Dimethyl(methanesulfinyl)sulfonium Hexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the Crystal Structure of Methanesulfinylchloride CH₃S(O)Cl [1] The preparation of dimethyl(methanesulfinyl)sulfoniumhexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the spectroscopic characterization of the new thiosulfonium salts are described. Alternatively they can be obtained from methylmethanethiosulfinate by methylation. In addition the crystal structure of methanesulfinylchloride CH₃S(O)Cl at 113 K is reported. The compound crystallizes in the monoclinic space group P2₁/n with a = 528.2(1), b = 829.2(2), c = 880.9(2) pm, β = 90.48(2)° and Z = 4.     

Bis(perfluor-n-hexyl)- und Bis(perfluor-n-octyl)cadmium: Darstellung,Eigenschaften, NMR-spektroskopische und massenspektrometrische Untersuchungen

Bis(perfluoro-n-hexyl) and Bis(perfluoro-n-octyl) Cadmium: Preparations, Properties, NMR Spectroscopic and Mass Spectrometric Investigations The perfluoroalkyl cadmium compounds Cd(C₆F₁₃)₂ and Cd(C₈F₁₇)₂ are isolated in pure states as well as complexes with dmf, CH₃CN, glyme, and diglyme. The reaction rate of Cd(R_f)₂ with PhHgCl increases with increasing dissociation, which is established by conductivity measurements. The NMR and the mass spectra are discussed.     

Synthetic,spectral, thermal and antimicrobial studies of bis(N,N‐dialkyldithiocarbamato)arsenic(III) and antimony(III) complexes with diphenyldithiophos‐phate and diphenyldithiophosphinate

Bis(N,N‐dialkyldithiocarbamato)arsenic(III)/antimony(III) diphenyldithiophosphate/diphenyldi‐thiophosphinate complexes of the type [R₂NCS₂]₂MS(S)PX₂ [where M = As and Sb; NR₂ = N(CH₃)₂, N(C₂H₅)₂ and N(CH₂)₄; X = OC₆H₅ and C₆H₅] have been synthesized and characterized by physico‐chemical, spectral [UV, IR and NMR (¹H, ¹³C and ³¹P)] and thermal (TG, DTA and DSC) analysis. The TG analysis shows single‐step decomposition of the complex to Sb₂S₃. These complexes have been screened for antibacterial and antifungal activity using the disc diffusion method. All the complexes have shown good activity as antibacterial and antifungal agents, which increased on increasing the concentration. Chloroamphenicol and terbinafin were used as standards for the comparison. Copyright © 2006 John Wiley & Sons, Ltd.     

Fluorination of perfluoroalkylsulfenyl chlorides,perfluorodialkyl disulfides and perfluorodialkyl sulfides with chlorine monofluoride

In reactions with perfluoroalkylsulfenyl chlorides (R_fSCl; R_f = F₃, C₂F₅, n-C₃F₇, n-C₄F₉) and perfluoroalkyl disulfides (R_fSSR_f′; R_f = R_f′ = CF₃, R_f = CF₃, R_f′ = C₂F₅) at 25°, chlorine monofluoride acts primarily as a chlorinating and fluorinating reagent to give the corresponding perfluoroalkylsulfur chloride tetrafluorides, R_fSF₄Cl, in good yields. However, small amounts of perfluoroalkylsulfur pentafluorides, R_fSF₅, are also obtained. A mixture of the cis and trans isomers of bis(trifluoromethyl)sulfur tetrafluoride and of trifluoromethyl pentafluoroethylsulfur tetrafluoride has been formed by the reaction of the corresponding bis(perfluoroalkyl) sulfides and chlorine monofluoride. The new perfluoroalkylsulfur chloride tetrafluorides are colorless, unpleasant smelling liquids. The infrared, mass and ¹⁹F NMR spectral data, as well as thermodynamic and elementary analysis data, are given for the new compounds.     

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.     

Fluorinated phosphorus compounds: Part 8. The reactions of bis(fluoroalkyl) phosphorochloridates with sulfur nucleophiles

The reactivity of bis(fluoroalkyl) phosphorochloridates to nucleophiles is summarised. Previous data and the results described here indicate that reactivities decrease in the order: amines>alcohols>thiols. The synthesis of CF₃CH₂OP(O)(SEt)₂ in 30% yield was accomplished by treating CF₃CH₂OP(O)Cl₂ with two molar equivalents of EtSH and Et₃N in ether. The chloridates (CF₃CH₂O)₂P(O)Cl and (C₂F₅CH₂O)₂P(O)Cl did not react with MeSH in ether at −78 °C or when heated with Pb(SMe)₂ in benzene. Ethanethiol and propanethiol reacted with fluorinated chloridates in the presence of triethylamine to give thiolates (R_FO)₂P(O)SR in 13-41% yield where R_F was CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂ or (CF₃)₂CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (R_FCH₂O)₂P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (R_FCH₂O)₂P(O)SPh in 43 and 46% yield where R_F was CF₃ and C₂F₅, respectively. Treatment of the chloridothiolate Cl(EtO)P(O)SMe, prepared in two steps from triethyl phosphite, with fluoroalcohols and triethylamine in ether gave species R_FO(EtO)P(O)SMe in 62-74% yield where R_F was CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂ or (CF₃)₂CH. The reactions of bis(trifluoroethyl) phosphorochloridate with 2-mercaptoethanol, 3-mercaptopropanol and ethane-1,2-dithiol gave several unexpected products whose structures were tentatively assigned.     

Perfluororganotellur-Verbindungen: Neue Untersuchungen zur Darstellung von Te(Rf)2 und CH3TeRf (Rf = C2F5, C3F7, C6F5)

Perfluoroorgano Tellurium Compounds: New Investigations on the Preparation of Te(R_f)₂ and CH₃TeR_f (R_f = C₂F₅, C₃F₇, C₆F₅) Methyl(perfluoroorgano) tellurium and bis(perfluoroorgano) tellurium compounds are synthesized in high yields from the photochemical or the thermal reactions of (CH₃)₂ Te with perfluoroorgano iodides in the presence of (C₂H₅)₃N. They are isolated in pure states. Another general method for the preparation of bis(perfluoroorgano) tellurium is the thermal reaction of TeCl₄ with bis(perfluoroorgano) mercury. The preparations and properties of the partially new compounds are described.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Zweikernige Palladium(II)‐, Platin(II)‐ und Iridium(III)‐Komplexe von Bis[imidazol‐4‐yl]alkanen

Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH₂)_n bridged imidazoles L(CH₂)_nL, n = 3–6) with chloro bridged complexes [R₃P(Cl)M(μ‐Cl)M(Cl)PR₃] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl₂(R₃P)M–L(CH₂)_nL–M(PR₃)Cl₂] 1 – 17 . The structures of [Cl₂(Et₃P)Pd–L(CH₂)₃L–Pd(PEt₃)Cl₂] ( 1 ), [Cl₂(Bu₃P)Pd–L(CH₂)₄L–Pd(PBu₃)Cl₂] ( 10 ), [Cl₂(Et₃P)Pd–L(CH₂)₅L–Pd(PEt₃)Cl₂] ( 3 ), [Cl₂(Et₃P)Pt–L(CH₂)₃L–Pt(PEt₃)Cl₂] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl₂(Cp*)Ir–L(CH₂)_nL–Ir(Cp*)Cl₂] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)₂Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).     

Darstellung und Eigenschaften von Dibromotrachloro-u-methylen- diantimonaten(III) and Hexabromotetrachloro-u-methylen-diantimonaten(V)

Preparation and Properties of Dibromotetrachloro-u-methylene-diantimonates(III) and Hexabromotetrachloro-u-methylene-diantimonates(V) The complex salts (R₄E)₂ [Br₃Cl₂Sb]₂ CH₂ (R₄E = Et₄N, Ph₄P, Ph₄As, Ph₄Sb) are obtained by the reaction of [Cl₂Sb]₂ with R₄ EBr in dichloromethane. The oxidation of the new compounds with Br₂ at ?78°C, in dichloromethane, leads to the corresponding complex salts of pentavalent antimony (R₄E)₂[Br₃Cl₂Sb]₂CH₂.     

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.     

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5)

Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgR_f, and perfluoroorgano cadmium compounds, Cd(R_f)₂, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅), and metal diethyldithiocarbamates, AgSC(S)N(C₂H₅)₂ and Cd[SC(S)N(C₂H₅)₂]₂. The mechanisms of the reactions with AgR_f and Cd(R_f)₂ are discussed.     

Kristall- und Molekülstruktur von fac-Trichloro-tris(dimethylsulfoxid)bismut(III) BiCl3(DMSO)3

Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl₃(DMSO)₃ Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH₃)₃SiN(SO₂CH₃)₂, BiCl₃, DMSO, CH₂Cl₂ and CH₃NO₂. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm³, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.     

Diimido‐, Imido(oxo)‐, Dioxo‐ und Imido(alkyliden)‐Halbsandwich‐Verbindungen über selektive Hydrolyse und α—H‐Abstraktion an Organylkomplexen des sechswertigen Molybdäns und Wolframs

Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η⁵‐C₅R₅)M(NR′)₂Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η⁵‐C₅R₅)M(NR′)₂Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η⁵‐C₅Me₅)M(NtBu)₂Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η⁵‐C₅Me₅)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η⁵‐C₅Me₅)M(O)₂(CH₃)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η⁵‐C₅H₅)W(NtBu)₂(CH₃)] and [(η⁵‐C₅Me₅)Mo(NtBu)₂(CH₃)] by HCl gas leads to [(η⁵‐C₅H₅)W(NtBu)Cl₂(CH₃)] 14 und [(η⁵‐C₅Me₅)Mo(NtBu)Cl₂(CH₃)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η⁵‐C₅R₅)M(NR′)Cl₃] with MeLi. As pure substances only trimethyl compounds [(η⁵‐C₅R₅)M(NtBu)(CH₃)₃] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η⁵‐C₅Me₅)M(NtBu)(CHPh)(CH₂Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η⁵‐C₅Me₅)M(NtBu)Cl₃] with PhCH₂MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]^2— > [O]^2— > [CHR]^2— ? 2 [CH₃]^— > 2 [Cl]^— emerges.