Seven-coordinate [ReVON4X2]+ complexes (X = O and Cl)

The oxorhenium(V) complexes with ligands containing N4 (H2pmen) and N4O2 (H2bbpen, H2Clbbpen, and H2bped) donor atom sets have been synthesized. X-ray crystallographic analyses of the [ReO(H2pmen)Cl2]+, [ReO(bbpen)]+, and [ReO(bped)]+ complexes showed that all three cations share a rare seven-coordinate structure with a distorted pentagonal bipyramidal geometry, which represents a novel and potentially general structural motif in ReV = O complexes. 1H NMR spectroscopy shows that the structures of the complexes are retained in the solution.     

Ionization of Ozone/Chlorofluorocarbon Mixtures in Atmospheric Gases: Formation and Dissociation of [CHX2O3]+ Complexes (X=Cl,F)

Complexes that undergo extensive molecular reorganization upon unimolecular metastable dissociation are obtained after ionization of atmospheric gases containing ozone and chlorofluorocarbons [Eq. (1)]. These unusual processes, which require fission of all bonds initially present in the CHX₂ unit (X=Cl, F) and combination of C with one of the O atoms of ozone, were demonstrated and their mechanism rationalized by the joint application of mass spectrometric and theoretical methods.     

Perfluoralkyltellur-Verbindungen: Untersuchungen zur Bildung von [(CF3)2TeX]+-Kationen und [(CF3)2TeX2+n]n−-Anionen (X = F,Cl, Br)

Perfluoroalkyl Tellurium Compounds: Investigations of the Preparation of [(CF₃)₂TeX]⁺ Cations and [(CF₃)₂TeX_2+n]^n? Anions (X = F, Cl, Br) The reactions of (CF₃)₂TeF₂ with BF₃, AsF₅ and SbF₅ yield the new complex compounds [(CF₃)₂TeF][BF₄] and [(CF₃)₂TeF][EF₆], respectively, while during the reactions of (CF₃)₂TeX₂ (X = Cl, Br) with halide acceptors only decompositions take place. (CF₃)₂TeX₂ form with MX (X = F, Cl; M = K, Rb, Cs, Me₄N, Ag) the isolable salts of the composition M[(CF₃)₂TeX₃]. M[(CF₃)₂TeBr₃] is only detected in solution besides decomposition products. No evidence for the formation of hexa-coordinated tellurates(IV) M₂[(CF₃)₂TeX₄] is found.     

Darstellung und Kristallstruktur von (NH4)2[V(NH3)Cl5]. Die Kristallchemie der Salze (NH4)2[V(NH3)Cl5], [Rh(NH3)5Cl]Cl2 und M2VXCl5 mit M = K,NH4, Rb,Cs und X = Cl,O

Preparation and Crystal Structure of (NH₄)₂[V(NH₃)Cl₅]. The Crystal Chemistry of the Compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂, and M₂VXCl₅ with M = K, NH₄, Rb, Cs and X ? Cl, O (NH₄)₂[V(NH₃)Cl₅] crystallizes like [Rh(NH₃)₅Cl]Cl₂ in the orthorhombic space group Pnma with Z = 4. The compounds are built up by isolated NH₄⁺ or Cl^? and complex MX₅Y ions. The following distances have been observed: V? N: 213.8, V? Cl: 235.8–239.1, Rh? N: 207.1–208.5, Rh? Cl: 235.5 pm. Both structures differ from the K₂PtCl₆ type mainly in the ordering of the MX₅Y polyhedra. The compounds M₂VCl₆ and M₂VOCl₅ with M = K, NH₄, Rb, and Cs crystallize with exception of the orthorhombic K₂VOCl₅ in the K₂PtCl₆ type. The ordering of the MX₅Y polyhedra in the compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂ and K₂VOCl₅ enables a closer packing.     

Bildung und NMR-spektroskopische Charakterisierung von Alk-(ar-)oxyderivaten von Trichlorphosphazen-N-phosphoryldichlorid,Cl3PN?P(O)Cl2, Imido- und N-Methylimidodiphosphoryltetrachlord,Cl2P(O)NHP(O)Cl2 bzw. Cl2P(O)N(CH3)P(O)Cl2

Formation and N.M.R.-Spectroscopic Characterization of Alk-(ar-)oxy Derivatives of Trichlorophosphazene-N-phosphoryldichloride, Cl₃P?N? P(O)Cl₂, Imido- and N-Methylimidodiphosphoryltetrachloride, Cl₂P(O)NHP(O)Cl₂ and Cl₂P(O)N(CH₃)P(O)Cl₂ The ester chlorides and esters P₂NOCl_5?x(OR)_x (x = 1?5), P₂(NH)O₂Cl_4?x(OR)_x (x = 1–4) and P₂(NCH₃)O₂Cl_4–x(OR)_x (x = 1–4) derived from the title compounds by substitution of chlorine atoms by alk- or aroxy groups are characterized by their ³¹P-n.m.r. data. The possibilities for forming these compounds by alcoholysis, chloridolysis, dealkylation and P? N-bond formation are discussed.     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

Gemischtligandkomplexe des Rheniums. V. Die Bildung von Nitrenkomplexen durch Kondensation von Aceton an koordinierten Nitridoliganden. Darstellung und Strukturen von fac-[Re{NC(CH3)2CH2C(O)CH3}X3(Me2PhP)2]-Komplexen (X = Cl,Br)

Mixed-ligand Complexes of Rhenium. V. The Formation of Nitrene Complexes by Condensation of Acetone at Coordinated Nitrido Ligands. Syntheses and Structures of fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] Complexes (X = Cl, Br) The reaction of rhenium(V)-mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] (HR₂tcb = N? (N,N-dialkylthiocarbamoyl)benzamidine) with HCl or HBr in acetone initializes a condensation of the solvent and results in nitrene-like compounds as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the condensed acetone. The chelate ligands are removed during this reaction and complexes of the type fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] (X = Cl, Br) are formed. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] crystallizes triclinic in the space group P1, a = 8.575(4); b = 9.088(3); c = 18.389(9) Å; α = 75.67(3)°, β = 85.30(3)°, γ = 70.58(4)°; Z = 2. A final R value of 0.031 was obtained on the basis of 6011 independent reflections with I ≥ 2σ(I). Rhenium is coordinated in a distorted octahedral environment with the three chloro ligands in facial positions. The rhenium-nitrogen bond (1,68(1) Å) is only slightly longer than typical Re? N bonding distances in nitrido complexes. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] is isomorphous with the chloro complex. Triclinic cell with a = 8.625(4); b = 9.198(3); c = 18.581(5) Å; α = 75.62(3)°, β = 85.40(3)°, γ = 70.91(3)°; Z = 2. The R value converged at 0.049 on the basis of 3644 independent reflections with I ≥ 2σ(I). fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] as well as fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] crystallizes in the noncentrosymmetric space group P1.     

Schwingungsspektren und Normalkoordinatenanalyse von (CF3)2PX und (CF3)2AsX (X = F,Cl, Br,J)

Vibrational Spectra and Normal Coordinate Analysis of (CF₃)₂PX and (CF₃)₂AsX (X = F, Cl, Br, I) Gas phase i. r. spectra and liquid-phase Raman spectra of (CF₃)₂AsX are reported. The i. r. investigation of the corresponding phosphorus compounds is complited. The spectra of both the phosphorus and the arsenic compounds were assigned on the basis of a normal coordinate analysis using a transferred force field.     

Synthese und Kristallstruktur von [Se3N2Cl]+ GaCl4−

Synthesis and Crystal Structure of [Se₃N₂Cl]⁺GaCl₄^? [Se₃N₂Cl]⁺GaCl₄^? has been prepared by the reduction of [Se₂NCl₂]⁺GaC1₄^? with SbPh₃ in CH₂Cl₂ solution, forming red crystals, which were characterized by an X-ray structure determination. Space group P2₁/n, Z = 4, 1640 observed unique reflections, R = 0.050. Lattice dimensions at ? 80 °C: a = 929.4(1), b= 1078.8(1), c = 1135.7(1) pm, β = 92.026(9)°. The cations from nearly planar Se₃N₂ five membered rings with Se? N bond lengths from 170 to 176pm and a Se? Se bond of 242.2 pm. One of the selenium atoms is bonded to the chlorine atom.     

[Mg3Cl5(Et2O)6]+: Darstellung,Strukturbestimmung und ab-initio-Untersuchungen

[Mg₃Cl₅(Et₂O)₆]⁺: Synthesis, Structure, and Ab-Initio Calculations The cation [Mg₃Cl₅(Et₂O)₆]⁺ of a chlorogallat has been prepared in a reaction of Ga₂Cl₄ with MgCp and was characterized by a X-ray single-crystal structure analysis. For understanding of the conditions of formation of neutral and charged magnesium chlorids and of the processes in the complex reaction system ab-initio calculations were performed.     

Synthese und Bau von (4-Picolinium)2[LnCl4(H2O)3]Cl (Ln = Eu,Ho)

Preparation and Structure of (4-Picolinium)₂[LnCl₄(H₂O)₃]Cl (Ln = Eu, Ho) The complex water containing chlorides (4-Picolinium)₂[LnCl₄(H₂O)₃]Cl (Ln = Eu, Ho) were prepared for the first time. The crystal structures were determined on single crystals by X-ray methods. The isotypic compounds crystallize with triclinic symmetry, space group P–1, Z = 2. Surprisingly the structures contain the complex anions [LnCl₄(H₂O)₃]^? (Ln = Eu, Ho) where the ligands form a distorted pentagonal bipyramid, which to our knowledge has not been observed in lanthanide compounds till now.     

Zum Ligandenaustausch an TcNX4−-Komplexen (X = Cl,Br)

Ligand-Exchange Reactions on TcNX₄^? Complexes (X = Cl, Br) Ligand exchange reactions on the nitridotechnetium(VI) compounds (Bu₄N)TcNCl₄ and (Bu₄N)TcNBr₄ are reported. The use of various organic ligands having different donor atom sets produces Tc^V nitrido complexes. The reaction of (Bu₄N)TcNCl₄ with (Bu₄N)TcNBr₄ is characterized by the formation of Tc^VI complex species with mixed Cl/Br coordination spheres. EPR detection of the mixed-ligand complexes results in a well-defined dependence of the EPR parameters on the composition of the first coordination sphere of the complexes.     

Insertion of H2C=CHX (X = F, Cl, Br, O(i)Pr) into (tBu3SiO)3TaH2 and beta-X-Elimination from (tBu3SiO)3HTaCH2CH2X (X = OR): relevance to Ziegler-Natta copolymerizations.

The insertion of H2C=CHX (X = OR; R = Me, Et, nPr, (i)Pr, CH=CH2, Ph) into (tBu3SiO)3TaH2 (1) afforded (tBu3SiO)3HTaCH2CH2X (2-CH2CH2X), which beta-X-eliminated to give ethylene and (tBu3SiO)3HTaX (3-X). beta-X-elimination rates were inversely proportional to the size of R. An X-ray crystallographic study of (tBu3SiO)3HTaCH2CH2O(t)Bu (2-CH2CH2O(t)Bu) revealed a distorted trigonal bipyramidal structure with an equatorial plane containing the hydride and a -CH2CH2O(t)Bu ligand with a staggered disposition. erythro- and threo-(tBu3SiO)3HTaCHDCHDOEt (2-CHDCHDOEt) are staggered in solution, according to (1)H NMR spectroscopic studies, and eliminated cis- and trans-HDC=CHD, respectively, helping verify the four-centered transition state for beta-OEt-elimination. When X = F, Cl, or Br, 2-CH2CH2X was not observed en route to 3-X, signifying that olefin insertion was rate-determining. Insertion rates suggested that substantial positive charge on the substituted carbon was incurred. The reactivity of other H2C=CHX with 1, and a discussion of the observations and their ramifications on the incorporation of functionalized monomers in Ziegler-Natta copolymerizations, are presented.     

Darstellung und Charakterisierung von [Pt(mal)2]2− und von trans-[Pt(mal)2X2]2− (X = Cl,Br, I,SCN)

Preparation and Characterization of [Pt(mal)₂]^2? and trans-[Pt(mal)₂X₂]^2? (X = Cl, Br, I, SCN) By twofold treatment of K₂[PtCl₄] with potassium hydrogen malonate in a queous solution the yellow K₂[Pt(mal)₂] · H₂O is obtained. After extraction with tetrabutylammonium ions into dichloromethane by oxidative addition at ?90°C the Pt^IV complexes [Pt(mal)₂X₂]^2?, X = Cl, Br, I, SCN, are formed. The SCN ligands are coordinated to Pt via S. The IR and Raman spectra are discussed and assigned.