Strukturen von neuen Bis(pentafluorophenyl)halogenomercuraten [{Hg(C6F5)2}3(μ‐X)]— (X = Cl,Br, I)

Structures of New Bis(pentafluorophenyl)halogeno Mercurates [{Hg(C₆F₅)₂}₃(μ‐X)]^— (X = Cl, Br, I) From the reactions of [PNP]Cl or [PPh₄]Y (Y = Br, I) with Hg(C₆F₅)₂ crystals of the composition [Cat][{Hg(C₆F₅)₂}₃X] (Cat = PNP, X = Cl ( 1 ); Cat = PPh₄, X = Br ( 2 ), I ( 3 )) are formed. 1 crystallizes in the triclinic space group P1¯, 2 and 3 crystallize isotypically in the monoclinic space group C2/c. In the crystals the halide anions are surrounded by three Hg(C₆F₅)₂ molecules. The reaction of [PPh₄]Br with Hg(C₆F₅)₂ under slightly changed conditions gives the compound [PPh₄]₂[{Hg(C₆F₅)₂}₃(μ‐Br)][{Hg(C₆F₅)₂}₂(μ‐Br)] ( 4 ).     

Syntheses and Properties of Tetrakis(pentafluorophenyl)tellurium,Te(C6F5)4, and Related Compounds — Single Crystal Structures of Tris(pentafluorophenyl)tellurium Bromide,Te(C6F5)3Br,Tris(pentafluorophenyl)tellurium Trifluoromethanesulfonate, [Te(C6F5)3][OSO2CF3], and Bis(pentafluorophenyl)tellurium Oxide,Te(C6F5)2O

Te(C₆F₅)₄ was prepared from the reactions of TeCl₄ or Te(C₆F₅)₂Cl₂ with Grignard reagents or AgC₆F₅ in moderate to good yields. Substitution reactions with Me₃SiX (X = Cl, Br, OSO₂CF₃), with equimolar amounts of Br₂, with AgNO₃ and with H[BF₄] or BF₃·OEt₂ yielded the Te(C₆F₅)₃X derivatives (X = Cl, Br, OSO₂CF₃, NO₃, BF₄). Oxidation reactions of Cd, Hg, and Pd⁰ complexes led to Te(C₆F₅)₂ and the corresponding bis(pentafluorophenyl) derivatives M(C₆F₅)₂ (M = Cd, Hg, Pd) and with InBr to In(C₆F₅)₂Br. From very slow hydrolysis of Te(C₆F₅)₄ the oxide Te(C₆F₅)₂O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C₆F₅)₃Br (monoclinic, P2₁/a, Z = 4), [Te(C₆F₅)₃][OSO₂CF₃] (monoclinic, P2₁/n, Z = 16) and [Te(C₆F₅)₂O]₂ (triclinic, P1¯, Z = 2) were determined.     

The Synthesis by Decarboxylation Reactions and Crystal Structures of 1, n–Bis(diphenylphosphino)alkane(pentafluorophenyl)‐platinum(II) Complexes

Decarboxylation reactions between the complexes cis–[PtCl₂L] (L = 1, n–bis(diphenylphosphino)–ethane (n = 2, dppe), –propane (n = 3, dppp) or –butane (n = 4, dppb)) and thallium(I) pentafluorobenzoate in pyridine give cis–[PtCl(C₆F₅)L] and cis–[Pt(C₆F₅)₂L] complexes in high yields with short reaction times. X–ray crystal structures of cis–[PtCl(C₆F₅)(dppe)] · 0.5 C₅H₅N, cis–[PtCl(C₆F₅)(dppp)], cis–[PtCl(C₆F₅)(dppb)] · C₃H₆O, cis–[Pt(C₆F₅)₂L] (L = dppe, dppp and dppb) and the reactants cis–[PtCl₂(dppp)] (as a CH₂Cl₂ solvate) and cis–[PtCl₂(dppb)] show monomeric structures with chelating diphosphine ligands in all cases rather than dimers with bridging diphosphines. ³¹P NMR data are consistent with these structures in solution.     

Synthesis and Crystal Structures of Lithium,Sodium, and ­Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

2‐(Methylthio)aniline (H₂L¹) and 2‐(phenylthio)aniline (H₂L²) were treated with n‐butyllithium to yield the corresponding anilides [LiHL¹] and [LiHL²]. Recrystallization from diethyl ether and THF afforded the solvates [LiHL¹(Et₂O)] and [LiHL²(THF)₂]. The X‐ray crystal structure determination revealed dimeric molecules which exhibit a centrosymmetric Li₂N₂ ring. In the case of [LiHL¹(Et₂O)] the SMe group is involved in Li coordination and in the case of [LiHL²(THF)₂] the SPh group is part of an intramolecular N–H ··· S hydrogen bridge. The sodium anilides [NaHL¹(DME)] and [NaHL²(DME)] were obtained from the reaction of H₂L¹ and H₂L² with sodium amide in DME as solvent. Like in the case of the lithium amides the sodium derivatives [NaHL¹(DME)] and [NaHL²(DME)] display centrosymmetric Na₂N₂ cores. The coordination sphere of the sodium atoms is completed by DME molecules, which act as chelating ligands. In the case of [NaHL¹(DME)] the DME molecules enable additionally a linkage of the dimeric subunits to give a chain structure. The potassium derivatives [KNHL¹] and [KNHL²(DME)] were obtained from H₂L¹ and H₂L² and potassium hydride in DME as solvent. [KNHL¹] displays a distinct structure based on [(KNHL¹)₂] dimers, which are linked by additional [KNHL¹] units to give a 3D coordination polymer with {4.8.16(3)} topology. [KNHL²(DME)] forms dimers linked by bridging DME molecules to give a chain‐like coordination polymer.     

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 Structure of [Methylzinc(2‐Pyridylethyl)(tert‐butyldimethylsilyl)amide] and its Hydrolysis Product

The metallation of (2‐pyridylethyl)(tert‐butyldimethylsilyl)amine ( 1 ) with dimethylzinc yields quantitatively dimeric methylzinc (2‐pyridylethyl)(tert‐butyldimethylsilyl)amide ( 2 ). Hydrolysis reactions lead to the precipitation of trakis(methylzinc) bis{2‐pyridylethyl)(tert‐butyldimethylsilyl}amide](μ₄‐oxide)] ( 3 ).     

Structural and Spectroscopic Characterization of Bis(thiosaccharinato)‐trispyridine‐cadmium(II)

The crystal structure of the title complex, [Cd(tsac)₂(py)₃], has been determined by single crystal X‐ray diffractometry. It crystallizes in the monoclinic space group C2/c with Z = 8.The Cd ²⁺ cation is at the center of a square‐ bipyramidal environment, equatorially coordinated to two thiosaccharinate anions through their sulfur atoms and the nitrogen atom of one of them acting as a bidentate ligand. Nitrogen atoms of pyridine molecules occupy the fourth equatorial position and the two axial ones. The infrared and electronic spectra of the complex were briefly discussed. Its thermal stability was investigated by thermogravimetric and differential thermal analysis.     

Structural Studies of Bis(cyclopentadienyl)molybdenum‐Amino Acid Complexes

The crystal structures of molybdocene‐amino acid compounds of the type [Cp₂Mo^IV(κN, κO‐AA)]⁺Cl^—·xH₂O with AA = D ‐phenylalaninato (x = 1.5), DL ‐leucinato (x = 2) and DL ‐valinato (x = 1) have been determined (Cp = η⁵‐C₅H₅). The compounds feature an almost planar, five‐membered chelate ring of the aminocarboxylate moiety (deprotonated amino acid) with the molybdenum atom. In the phenylalaninato complex π‐stacking between the phenyl rings is found. The complexes were proven kinetically stable at pH < 1 for at least 24 h.     

Syntheses and Structural Characterization of Four New Silver(I) Complexes with the N,N′(O)‐bidentate Bridging Ligands

Four new bridged silver(I) complexes, namely [Ag₂(μ₂‐teda)(μ₂‐fbc)₂] ( 1 ), [Ag₂(μ₂‐1,6‐dah)₂](bpdc) · 4H₂O ( 2 ), [Ag₂(μ₂‐2‐ap)(2‐ap)(bnb)] · 0.34H₂O ( 3 ), [Ag₂(μ₂‐pyc)₂(2‐apy)₂] · 0.5H₂O ( 4 ), have been synthesized and characterized by elemental analysis and crystallographic methods [fbc = 4‐fluorobenzoate, teda = triethylenediamine ( 1 ); bpdc = biphenyl‐4,4′‐dicarboxylate, 1,6‐dah = 1,6‐diaminohexane ( 2 ); bnb = 3,5‐binitrobenzoate, 2‐ap = 2‐aminopyrimidine ( 3 ); pyc = 3‐pyridinecarboxylate acid, 2‐apy = 2‐aminopyridine ( 4 )]. Complex 1 contains a 1D linear chain paralleling to the c‐axis, whereas in complex 2 silver(I) atoms were bridged by the 1,6‐dah ligand into a zigzag chain, further giving a 1D ribbon by weak Ag ··· Ag interactions. Complex 3 consists of a dinuclear silver(I) [Ag₂(μ₂‐2‐ap)(2‐ap)(bnb)] moiety and a lattice water molecule, forming a 3D network via a number of hydrogen‐bonding interactions such as N–H ··· O, N–H ··· N and C–H ··· O hydrogen bond and other weak interactions such Ag ··· Ag, Ag ··· N, N ··· O as well as O ··· O interaction. Similar to 3 , the asymmetric unit of 4 consists of one dinuclear silver(I) [Ag₂(μ₂‐pyc)₂(2‐apy)₂] moiety and half lattice water molecule, further generating a tetranuclear silver(I) {[Ag₂(μ₂‐pyc)₂(2‐apy)₂]₂ · H₂O} moiety. These moieties construct a 3D supramolecular network structure of 4 through N–H ··· O, O–H ··· O and C–H ··· O hydrogen bonds as well as other weak interactions such as Ag ··· O and N ··· O interactions.     

Synthesis,Structural Characterization and Physical Properties of a New Member of Ternary Lithium Layered Compounds – Li2RhO3

Li₂RhO₃ was synthesized by solid state reaction and its crystal structure was refined from X‐ray powder data by the Rietveld‐method. The compound was obtained as a black powder and crystallizes in the monoclinic space group C2/m, with unit cell parameters a = 5.1198(1), b = 8.8497(1), c = 5.1030(1) Å, β = 109.61(2) °, V = 217.80(1), and Z = 4. The structure determination shows that the oxygen atoms in Li₂RhO₃ form an approximate cubic close packing, where all octahedral voids are occupied by Rh⁴⁺ and Li⁺ cations. The structure is closely related to the α‐NaFeO₂ and Li₂MnO₃ layered structure types (layered variants of the NaCl‐type), but in Li₂RhO₃ the lithium and rhodium atoms are partially disordered. Li₂RhO₃ behaves as a semiconductor with rather small activation energy of 7.68 kJ · mol^–1 and is thermally stable up to 1273 K in argon atmosphere. According to measurements of the magnetic susceptibility in the temperature range from 2 to 330 K, Li₂RhO₃ is paramagnetic, obeys the Curie–Weiss law at temperatures above 150 K, and has an effective magnetic moment of 1.97 μ_B at 300 K.     

两个含N-皮考林酰肼铁配合物的合成和结构表征

合成了含N-乙酰皮考林酰肼(简写为Haphz)的铁配合物[Fe₂(aphz)₂(μ-CH₃O)₂Cl₂]·CH₃OH(1,C₁₉H₂₆Cl₂Fe₂N₆O₇,Mr=633.06)和含N-苯甲酰皮考林酰肼(简写为Hphphz)的铁配合物Fe(phphz)Cl₂(2,C₁₃H₁₀Cl₂FeN₃O₂,Mr=366.99).2个配合物均属三斜晶系,空间群为P     

Molecular and Crystal Structures of Pentafluorophenyl‐platinum(II) Complexes with Bis(diphenylphosphino)methane,Bis(diphenylarsino)methane and 1,2‐Bis(diphenylarsino)ethane

The X‐ray crystal structures of [PtCl₂(dppm)], [Pt(C₆F₅)₂L] (L = dppm (bis(diphenylphosphino)methane), dpam (bis(diphenylarsino)methane), dpae (bis(diphenylarsino)ethane)) and [PtCl(C₆F₅)(dpae)] show the complexes to be monomeric with chelating dipnictido ligands, and not alternatives with bridging ligands. In [Pt(C₆F₅)₂(dpam)₂], there are two unidentate diarsine ligands in a cis‐arrangement.     

Oxidative C‐C Coupling of Dilithium (2‐Pyridylmethanidyl)(tert‐butyldimethylsilyl)amide with White Phosphorus

(2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amine ( 1 ) can be lithiated once or twice yielding lithium (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amide ( 2 ) and dilithium (2‐pyridylmethanidyl)(tert‐butyldimethylsilyl)amide ( 3 ), respectively. The oxidation of 3 with white phosphorus yields dilithium 1,2‐dipyridyl‐1,2‐bis(tert‐butyldimethylsilylamido)ethane ( 4 ) which crystallizes after partial hydrolysis as an adduct of the form 2 · 4 .     

Structural Characterization of Mn2+—ß″—Al2O3(Mn0.77Al10.46Mg0.54O17)

The structure of completely exchanged Mn²⁺—ß″—Al₂O₃(Mn_0.77Al_10.46Mg_0.54O₁₇) crystals has been investigated by single—crystal X—ray diffraction methods at room temperature (trigonal, R3¯, Z = 3, a = 560.65(7), c = 3329.3(9) pm). The manganese ions (Mn²⁺) are found to occupy Beevers‐Ross (56 %) and mid—oxygen positions (44 %) in nearly the same amounts. The crystal composition was confirmed by electron probe microanalyses on various crystals.     

Silver Compounds in Synthetic Chemistry. 1 A Facile Preparative Route for Pentafluorophenylsilver,AgC6F5 and its Use as an Oxidative Pentafluorophenyl Group Transfer Reagent in Reactions with Group 12 to 16 Elements — the Single Crystal Structure of AgC6F5 · EtCN,the First Arylsilver Derivative Crystallising in Infinite Chains

AgC₆F₅ is directly and quantitatively formed from room temperature reactions of AgF and Me₃SiC₆F₅ in N‐donor solvents, particularly EtCN. Solutions of AgC₆F₅ prepared by this method exhibit excellent oxidative properties in reactions with a variety of groups 12 to 16 elements giving the corresponding pentafluorophenyl element compounds in moderate to excellent yields. AgC₆F₅·EtCN crystallises with monoclinic symmetry (C2/c, Z = 8, a = 2301.4(5) pm, b = 1078.8(4) pm, c = 948.0(2) pm, β = 113.19(1)°) and exhibits chains of silver atoms with bridging C₆F₅ groups.     

Synthesis and Structural Characterization of two Novel Copper(I) Complexes with Oxygen Donor

Two novel copper(I) complexes with Cu‐O bonds, [Cu₂L₂(PPh₃)₂](BF₄)₂ ( 1 ) and [Cu(L)(dppeo)](BF₄) ( 2 ) ( L = 6‐(4‐diethylmethylphosphonatephenyl)‐2,2′‐bipyridine, dppeo = bis(diphenylphosphino)ethane monoxide), have been prepared and their structures characterized. In the binuclear complex 1 , the ligand L serves as tridentate donor with the N, N′ and O as coordination atoms, and the two Cu^I atoms are bridged through both P = O donor atoms in different ligand L with a triphenylphosphine molecule as auxiliary ligand. While in mononuclear complex 2 , both ligands L and dppeo behave as bidentate with N^∧N from L and P^∧O from dppeo chelating to Cu^I atom.     

两个含双(3,5－二甲吡唑基)甲烷配体的铅(II)配合物的合成与结构表征

Reactions of lead（Ⅱ） nitrate or perchlorate with bis（3,5-dimethylpyrazolyl）methane （dmpzm）, produced two new Pb（Ⅱ） chelated complexes [Pb（dmpzm）2X2] （X=NO3^- 1, ClO4^- 2）. Both compounds were structurally characterized by elemental analysis, IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. Both compounds are mononuclear with a distorted square antiprismatic PbN4O4 coordination geometry incorporating a pair of O,O＇-bidentate anions and N,N＇-bidentate dmpzm ligands. In the crystals of 1 or 2, the methyl or methylene groups of dmpzm ligand interact with the oxygen atoms of nitrates or perchlorates to afford intra- and intermolecular hydrogen bonding, thereby forming a two-dimensional network 1 or a three-dimensional structure 2.     

Cobalt(II) Complexes with Dicyanamide — from Binuclear Entities to Chains

One binuclear complex [Co(bpm*)₂(dca)]₂(ClO₄)₂ ( 1 ) and two 1D chain Co^II complexes, {[Co(bpm)₂(dca)](ClO₄)}_n ( 2 ) and [Co(dmf)₂(dca)₂]_n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R₁ = 0.0672, wR₂ = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each Co^II ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R₁ = 0.0609, wR₂ = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of Co^II ions bridged by one dca ligand. Each Co^II ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C₂, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R₁ = 0.0260, wR₂ = 0.0760. 3 has a one‐dimensional linear chain of Co^II ions bridged by two dca ligands, in which each Co^II ion is coordinated with two dmf molecules.     

Syntheses and X‐Ray Crystal Structures of [Li(thf)4][SnCl5(thf)] and {[Li(Et2O)2]2‐(μ‐Cl2)2‐SnIVCl2}

The syntheses and single crystal X‐ray structure determinations are reported for [Li(thf)₄][SnCl₅(thf)] ( 1 ) and {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} ( 2 ). Compound 1 is ionic with a tetrahedral coordinated lithium cation and distorted octahedral tin (IV) atom in the anion, while compound ( 2 ) is a centrosymmetric heteronuclear double salt of LiCl and SnCl₄. [Li(thf)₄][SnCl₅(thf)] is monoclinic, P2₁/n, a = 11.204(1), b = 15.599(1), c = 17.720(2) Å; β = 96.734(2)°, Z = 4, R 0.0418; {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} is monoclinic, P2₁/n, a = 10.848(2), b = 12.764(2), c = 11.748(2) Å; β = 90.388(3)°, Z = 4, R = 0.0851.     

Structural Investigation of New Lithium Amidinates and Guanidinates

A series of potentially useful lithium amidinates and guanidinates were prepared and fully characterized. Treatment of N,N′‐diisopropylcarbodiimide with phenyllithium in diethyl ether afforded the lithium amidinate [PhC(NiPr)₂Li(OEt₂)]₂ ( 1 ). Similar treatment of N,N′‐diorganocarbodiimides R′–N=C=N–R′ [R′ = iPr, cyclohexyl (Cy)] with secondary lithium amides LiNR₂ [R₂ = Et₂, iPr₂, (CH₂)₄] followed by crystallization from THF or 1,4‐dioxane gave the lithium guanidinates [R₂NC(NR′)₂Li(S)]₂ [ 2 : R = Et, R′ = iPr, S = THF; 3 : R₂ = (CH₂)₄, R′ = iPr, S = THF; 4 : R = R′ = iPr, S = ½ 1,4‐dioxane; 5 : R₂ = (CH₂)₄, R′ = Cy, S = 1,4‐dioxane] as crystalline solids. Reaction of N‐lithioaziridine with the corresponding carbodiimides afforded solvent‐deficient [{C₂H₄NC(NiPr₂)₂}₂Li₂(THF)]₂ ( 6 ), and [C₂H₄NC(NEt)(NtBu)Li(THF)]₂ ( 7 ). Crystal structure determination revealed the presence of common ladder‐type dimeric structures for 1 – 5 . Compound 6 exists as a dimer of two ladder‐type dimers in the crystal, and 7 exhibits an unusual dimeric structure comprising an eight‐membered C₂N₄Li₂ ring.