A Convenient,Selective Synthesis of Bis[2,4‐bis(trifluoromethyl)phenyl]phosphane Derivatives Starting from 1,3‐Bis(trifluoromethyl)benzene

The reaction of the sterically shielded phosphane derivative, dichlorodiethylaminophosphane, Cl₂PNEt₂, with an excess of a mixture of 2,6‐bis(trifluoromethyl) and 2,4‐bis(trifluoromethyl)phenyl lithium gives bis[2,4‐bis(trifluoromethyl)phenyl]diethylaminophosphane, [2,4‐(CF₃)₂C₆H₃]₂PNEt₂, in 72 % yield as a colourless solid, while 2,6‐bis(trifluoromethyl)phenyl lithium remains unchanged in solution. The amino derivative crystallizes in the monoclinic space group P2₁/c (a 869.2(1), b 1857.4(1), c 1357.6(1) pm, β 100.57(4)°, Z = 4). Treatment of [2,4‐(CF₃)₂C₆H₃]₂PNEt₂ in CHCl₃ solution with conc. HCl allows the synthesis of [2,4‐(CF₃)₂C₆H₃)]₂PCl. [2,4‐(CF₃)₂C₆H₃]₂PCl reacts with H₂O in THF solution with quantitative formation of the corresponding secondary phosphane oxide. To obtain bis[2,4‐bis(trifluoromethyl)phenyl]phosphinic acid, [2,4‐(CF₃)₂C₆H₃]₂P(O)OH, quantitatively, a CHCl₃ solution of [2,4‐(CF₃)₂C₆H₃]₂P(O)H, has to be stirred in an NO₂ atmosphere. The phosphinic acid crystallizes is the triclinic space group (a 754.2(1), b 927.6(2), c 1305.5(2) pm, α 85.11(2)°, β 75.45(1)°, γ 79.99(2)°, Z = 2). From the reaction of the phosphinic acid with either elemental sodium or with cyanide salts, the corresponding phosphinate salts are obtained in an almost quantitatively yield.     

Synthesis and Structural Characterization of Bis(tetrahydro­pyran)calcium Bis[bis(trimethylsilyl)amide]

Transmetalation of Sn[N(SiMe₃)₂]₂ with calcium granules in tetrahydropyran (thp) yields colorless [(thp)₂Ca{N(SiMe₃)₂}₂] ( 1 ) which is soluble in common organic solvents. The calcium center is in a distorted tetrahedral environment with Ca–N and Ca–O bond lengths of 231.08(11) and 240.23(9) pm, respectively. The molecular structure is dominated by steric factors leading to a NCaN bond angle of 119.43(6)°.     

Synthesis and Crystal Structures of Mixed Halophenylbismuthates(III)

Synthesis and characterisation of mixed halophenylbismuthates(III) with a general formula Bu₄N[PhBiX₂Y] where X = Cl or Br; Y = Cl, Br or I; X ≠ Y are reported. The molecular structures of Bu₄N[PhBiCl₂Br] ( 1 ) and Bu₄N[PhBiBr₂I] ( 2 ) are determined by X‐ray crystallography. In mixed halophenylbismuthates, the anion exists as a dimer with bismuth in a distorted square pyramidal coordination. In the dimer the two phenyl groups occupy anti position to each other thereby minimising the repulsion.     

Hydrothermal Synthesis and Crystal Structure of CaIn2(PO4)2(HPO4): An octahedral-tetrahedral framework ternary calcium indium(III) phosphate

The new ternary calcium indium(III) phosphate CaIn₂(PO₄)₂(HPO₄) with mixed octahedral-tetrahedral framework was synthesized through hydrothermal reaction of stoichiometric amounts of CaO and InCl₃ with excess of H₃PO₄ and H₂O at pH = 1. Single crystal x-ray diffraction studies show the compound to crystallize in monoclinic symmetry, space group P2₁/n (#14) with a = 657.08(6), b = 2023.7(2), c = 665.72(7) pm, β = 91.20(1)°, Z = 4 and R = 0.043. The framework is built up of dimers of edge-sharing InO₆ octahedra forming In₂O₁₀ units sharing all their OXO ligands with PO₄ tetrahedra, and HPO₄ groups.     

Synthesis of Phosphanes Bearing 2‐Imino‐1,3‐thiazolidine Ligands – X‐Ray Analyses and NMR Spectroscopy

Pseudo‐ephedrine derived 2‐imino‐1,3‐thiazolidine 1 reacts with tris(diethylamino)phosphane by stepwise replacement of the diethylamino group to give the mono‐, bis‐ and tris(imino)phosphanes 2 , 3 and 4 , respectively, of which 4 could be isolated in pure state. The analogous reaction with diethylamino‐diphenylphosphane affords the imino‐diphenylphosphane 5 . The iminophosphanes react with sulfur or selenium to give the corresponding phosphorus(V) compounds. In contrast, the reaction of the iminophosphanes with oxygen is very slow; anhydrous trimethylamine N‐oxide reacts in the melt with the phosphanes to give the oxides 4(O) and 5(O) . The molecular structures of 4(O) (in mixture with 4 ), 4(Se) , 5(S) and 5(Se) were determined by X‐ray analysis. In all cases the ring‐sulfur and the phosphorus atoms are in cis‐positions at the C=N bonds. The analogous solution structures were determined by ¹H, ¹³C, ¹⁵N, ³¹P and ⁷⁷Se NMR spectroscopy. In the case of the compounds 5 , 5(O) , 5(S) and 5(Se) the isotope‐induced chemical shifts ¹δ^14/15N(³¹P) were determined, using INEPT‐HEED experiments.     

Zur Strukturchemie der Alkyl- und Arylhalogenoarsenate(III), [Me2As2Cl5]–, [RAsCl3]–, [R2As2Br6]2– (R = Me,Et, Ph) und [Ph2AsX2]– (X = Cl,Br)

Structural Chemistry of the Alkyl- and Arylhaloarsenates(III) [Me₂As₂Cl₅]^–, [RAsCl₃]^–, [R₂As₂Br₆]^2– (R = Me, Et, Ph) and [Ph₂AsX₂]^– (X = Cl, Br) The alkyl- and arylhaloarsenates(III) [Ph₄P][Me₂As₂Cl₅] ( 1 ), [Ph₄P][RAsCl₃] (R = Me, Et, Ph, 2 – 4 ), [Me₃PhN][PhAsCl₃] ( 5 ), [Ph₄P]₂[R₂As₂Br₆] (R = Me, Et, Ph, 6 – 8 ), [n-Pr₄N][Ph₂AsCl₂] ( 9 ) and [n-Bu₄N][Ph₂AsBr₂] ( 10 ) have been prepared and their structures established by X-ray diffraction. In contrast to the chloroarsenates(III) 2 – 5 , which all contain isolated ψ-trigonal bipyramidal anions [RAsCl₃]^–, the analogous bromoarsenates(III) 6 – 8 exhibit dimeric structures. Whereas the trans sited As–Cl distances in 2 and 3 are very similar a pronounced degree of asymmetry is apparent for the Cl–As–Cl three-centre bonds in 4 and 5 [2.396(1) and 2.602(1) Å in 5]. In 6 and 7 C_i symmetry related RAsBr₂ units are connected through long As…Br bonds [2.926(1) and 3.116(2) Å in 6 ]. The bromophenylarsenate(III) anion of 8 which contains two effectively undistorted ψ-trigonal bipyramids [PhAsBr₃]^– associated by weak As…Br interactions [3.117(2) Å]. In view of its very long bridging As…Cl distances the [Me₂As₂Cl₅]^– anion in 1 can, as 6 an 7 , be regarded as two MeAsCl₂ molecules weakly linked through a chloride ion.     

The First Aqua Pentafluoro Manganates(III) – Syntheses and Structures

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH₂[MnF₅(H₂O)] · H₂O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P2₁/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH₂ · [MnF₅(H₂O)] · H₂O 2 (NMpipz = N-Methylpiperazine), space group P2₁/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH₂[MnF₅(H₂O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH₂[MnF₅(H₂O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF₅(H₂O)]^2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented.     

Phenyliodine(III) Bis(Trifluoroacetate) Mediated Synthesis of 2‐Aryl‐1,2‐Benzisothiazol‐3(2H)‐Ones in Ionic Liquid

Treatment of N‐aryl‐2‐(benzylthio)benzamides with phenyliodine(III) bis(trifluoroacetate) containing trifluoroacetic acid resulted in an interrupted Pummerer‐type reaction in ionic liquid 1‐n‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim][PF₆] to give 2‐aryl‐1,2‐benzisothiazol‐3(2H)‐ones rather than the normal Pummerer‐type products.     

Synthesis and Crystal Structure of a Binuclear Gadolinium(III) Complex Bridged by Cucurbit[6]uril

Cucurbit[6]uril (Q6, Figure 1) is a macrocyclic ligand with interesting complexing properties. In contrast to other macrocyclic ligands, such as crown ethers, cryptands or calixarenes, this ligand has a rigid structure offering a hollow core of about 5.5 …     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Bis(trimethylsilyl)amide und -methanide des Yttriums — Molekülstrukturen von Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl) methyl]yttriat,solvensfreiem Yttrium-tris[bis(trimethylsilyl)amid] sowie dem Bis(benzonitril)-Komplex

Bis(trimethylsilyl)amides and -methanides of Yttrium — Molecular Structures of Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl)methyl]yttriate, solvent-free Yttrium Tris[bis(trimethylsilyl)amide] as well as the Bis(benzonitrile) Complex The reaction of yttrium(III) chloride with the three-fold molar amount of LiE(SiMe₃)₂ (E = N, CH) yields the corresponding yttrium derivatives. Yttrium tris-[bis(trimethylsilyl)amide] crystallizes in the space group P3 1c with a = 1 636,3(2), c = 849,3(2) pm, Z = 2. The yttrium atom is surrounded trigonal pyramidal by three nitrogen atoms with Y? N-bond lengths of 222 pm. Benzene molecules are incorporated parallel to the c-axes. The compound with E = CH crystallizes as a (Et₂O)₃LiCl-adduct in the monoclinic space group P2₁/n with a = 1 111,8(2), b = 1 865,2(6), c = 2 598,3(9) pm, β = 97,41(3)° and Z = 4. The reaction of yttrium tris[bis(trimethylsilyl)amide] with benzonitrile yields the bis(benzonitrile) complex, which crystallizes in the triclinic space group P1 with a = 1 173,7(2), b = 1 210,3(2), c = 1 912,4(3) pm, α = 94,37(1), β = 103,39(1), γ = 117,24(1)° and Z = 2. The amido ligands are in equatorial, the benzonitrile molecules in axial positions.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse der bindungsisomeren Chlororhodanoiridate(III) trans-[IrCl2(SCN)4]3− und trans-[IrCl2(NCS)(SCN)3]3−

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? By treatment of Na₂[IrCl₆] with NaSCN in 2N HCl the linkage isomers trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu₄N)₃[IrCl₂(SCN)₄] ( 1 ) (monoclinic, space group P2₁/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me₄N)₃[IrCl₂(NCS)(SCN)₃] ( 2 ) (monoclinic, space group P2₁/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are f_d(IrS) = 1.52 and f_d(IrCl) = 1.72 mdyn/Å.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Structural studies of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine hetero‐scorpionate copper complexes

The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the Cu^I and Cu^II oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C₁₅H₁₇N₃)]·0.18H₂O, (1), catena‐poly[[copper(I)‐μ₂‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ⁵N,N′,N′′:C²,C³] perchlorate acetonitrile monosolvate], {[Cu(C₁₅H₁₇N₃)]ClO₄·CH₃CN}_n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl₂(C₁₅H₁₇N₃)]·CH₂Cl₂, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) perchlorate, [CuCl(C₁₅H₁₇N₃)]ClO₄, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu₂Cl₂(C₁₅H₁₇N₃)₂][(C₆H₅)₄B]₂, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu^I complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu^I atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with Cu^II show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu₂Cl₂ moiety.     

Synthesis and magnetism of the first tetranuclear copper(II)–iron(III) complexes of macrocyclic oxamides

Four novel tetranuclear macrocyclic complexes of the formula [(CuLⁱ)₃Fe](ClO₄)₃·3H₂O (i=1–4, Lⁱ are the dianions of the [14]N₄ and [15]N₄ macrocyclic oxamides, namely 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene, 2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene and 2,3-dioxo-5,6:14,15-dibenzo-7,13-bis(ethoxycarbonyl)-1,4,8,12-tetraazacyclotetradeca-7,12-diene] have been prepared and characterized. These complexes are the first examples of oxamido-bridged Cu(II)–Fe(III) heterometallic species. Cryomagnetic studies on [(CuL¹)₃Fe](ClO₄)₃·3H₂O (1) and [(CuL³)₃Fe](ClO₄)₃·3H₂O (3) (77–300 K) revealed that the Cu(II) and Fe(III) ions interact antiferromagnetically through the oxamido bridge, with the exchange integral J=−30.8 cm⁻¹ for 1 and J=−28.7 cm⁻¹ for 3 based on . The interaction parameters have been compared with that of the related [Cu₃Mn] compound.     

Ca[PO2(NH)3(CO)2]2 – The First Biuretooxophosphate with a Divalent Cation

Calcium biuretooxophosphate Ca[PO₂(NH)₃(CO)₂]₂ was synthesized by ion exchange reaction in aqueous solution. The crystal structure of the salt was elucidated by single‐crystal X‐ray diffraction. Anionic 1‐phospha‐2, 4, 6‐s‐triazine rings exhibiting a half‐chair conformation act as monodentate ligands for the calcium ions. A 3D network is formed by the resulting CaO₆ octahedrons together with the anionic rings interconnected by hydrogen bonds. Beside the crystal structure, FTIR and photoluminescence spectra of calcium biuretooxophosphate are discussed. The thermal behavior of the salt is examined by means of temperature‐dependent powder X‐ray diffraction measurements and combined TG and DTA analyses.     

Regioselective Synthesis of 5‐(2‐Cyanoethyl)‐1,1′‐biphenyl‐2‐carboxylates by Formal [3+3] Cyclocondensations of 1,3‐Bis[(trimethylsilyl)oxy]buta‐ 1,3‐dienes

5‐(2‐Cyanoethyl)‐1,1′‐biphenyl‐2‐carboxylates were prepared by regioselective formal [3+3] cyclocondensations of 1,3‐bis[(trimethylsilyl)oxy]buta‐1,3‐dienes.     

Structures involving unshared electron pair. The Crystal Structures of As(OCOCH3)3 and As2O(OCOCH3)4

As₂O(OCOCH₃)₄, reported now for the first time, was obtained, besides As(OCOCH₃)₃ by dissolving As₂O₃ in acetic anhydride. The crystals of As(OCOCH₃)₃ (A) (monoclinic, space group Cc, Z = 4, a = 9.970(2), b = 13.203(2), c = 8.272(1) Å, β = 117.01(2)°) and of As₂O(OCOCH₃)₄ (B) (monoclinic, space group P2₁/n, Z = 4, a = 13.966(5), b = 8.127(4), c = 12.706(4) Å, β = 95.14(1)°) are built up from discrete molecules defined by chemical formulae As(OCOCH₃)₃ and (CH₃OCO)₂As? O? As(OCOCH₃)₂, respectively. The molecular structure of both compounds is based on the AsO₃ pyramid: in (A) with the As? O bonds of 1.841(6) Å and the O? As? O angle of 89.9(3)° as a mean, in (B) with slightly different values and with the As? O? As angle of 127.7(4)° at the bridging oxygen atom. The additional weak chelating contacts are at the distances As…O from 2.625(9) to 2.745(10) Å in (A) and from 2.72(1) to 2.84(2) in (B). The actual arsenic coordination can be described as very distorted octahedral in (A) and square-pyramidal in (B).     

Cyclische Phosphidostannat(III)-Anionen [Sn12P24]36– in Sr3[Sn2P4]

Cyclic Phosphidostannate(III) Anions [Sn₁₂P₂₄]^36– in Sr₃[Sn₂P₄] The metallic lustrous, air sensitive compound Sr₃[Sn₂P₄] was prepared from melts of mixtures of the elements. Sr₃[Sn₂P₄] crystallizes in the orthorhombic system, space group Cmca (a = 2510,4(9), b = 1259,3(6), c = 1869,3(8), Z = 24). In the anionic partial structure six moieties [Sn₂P₆] isostructural to Si₂Cl₆ are linked by each four common P-ligands forming cyclic units [Sn₁₂P₂₄]^36–. The strontium cations are octahedrally coordinated by P. The arrangement can be described as a distorted cubic close packing of P^3– in which in an ordered manner ³/₄ of the octahedral vacancies are occupied by Sr²⁺ and ¹/₄ by Sn₂-dumbbells.