Magnesiumphthalocyanine: Darstellung und Eigenschaften von Halogenophthalocyaninatomagnesat, [Mg(X)Pc2−]− (X = F,Cl, Br); Kristallstruktur von Bis(triphenylphosphin)iminiumchloro(phthalocyaninato)magnesat-Aceton-Solvat

Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc^2?]^? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((ⁿBu₄N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc^2?]^?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (ⁿBu₄N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of ^b(PNP)[Mg(Cl)Pc^2?] · CH₃COCH₃ reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N_iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? N_iso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (^b(PNP)⁺: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.     

Monomeric five-coordinate rhenium diazenido and hydrazido complexes with aromatic thiolate ligands: X-ray structures of [Re(NNC6H4-Br)2(SC6H3-2,5-Me2)(PPh3)2] and [ReO(NNMePh)(SPh)3], and of the synthetic precursor [Re(NNC6H4-4-Br)2Cl(PPh3)2]

Reaction of [ReOCl₃(PPh₃)₂] with bromophenylhydrazine in methanol yields [ReCl(N₂C₆H₄Br)₂(PPh₃)₂] (1). Complex 1 reacts with arylthiolates to give mixtures of [Re(SAr)(N₂C₆H₄Br)₂(PPh₃)₂] (2) and [Re₂(SAr)₇(NNR)₂]⁻. Complexes 1 and 2 display trigonal bipyramidal geometries with the phosphine ligands occupying the axial sites. A significant feature of the structures is the nonequivalence of the rhenium-diazenido moieties, such that for 1 the ReN(1) and N(1)N(2) distances are 1.80(2) and 1.24(3) Å, while ReN(3) and N(3)N(4) are 1.73(2) and 1.32(3) Å, and for 2 the ReN distances are 1.73(1) and 1.80(2)° with corresponding NN distances of 1.32(2) and 1.25(2) Å. Reaction of (PPh₄)[ReO(SPh)₄] (3) with unsymmetrically disubstituted hydrazines affords complexes of the type [ReO(SPh)₃(NMRR′)] (R = Me, R′ = Ph for 4). Complexes 3 and 4 display distorted square pyramidal geometries with the oxo groups apical. The significant feature of the structure of 4 is the nonlinear ReN(1)N(2) linkage, exhibiting an angle of 145.6(10)°. The angle does not appear to correlate with a significant contribution from a valence form with sp² hybridization at the α-nitrogen. Crystal data: 1: monoclinic space group, P2₁/n, a = 12.216(2) Å, b = 19.098(2) Å, c = 20.257(4) Å, β = 106.20(1)°, V = 4538.3(8) ų to give Z = 4; structure solution and refinement based on 1905 reflections converged at R = 0.070. 2: monoclinic space group P2₁/n, a = 14.393(2) Å, b = 18.842(3) Å, c = 20.717(4)Å, β = 110.26(1)°, V = 5270.5(8) ų to give Z = 4 for D = 1.53 g cm⁻¹; structure solution and refinement based on 4249 reflections to give R = 0.070. 3: monoclinic space group P2₁/n, a = 12.531(2) Å, b = 24.577(4) Å, c = 16.922(3) Å, β = 99.06(1)°, V = 5146.2(9) ų, D = 1.36 g cm⁻³ for Z = 4, 2912 reflections, R = 0.050. 4: monoclinic space group p2₁/n, a = 16.137(2) Å, b = 9.863(2) Å, c = 16.668(2) Å, β = 111.12(1)°, V = 2474.7(6) ų, D = 1.74 g cm⁻³ for Z = 4, 2940 reflections, R = 0.066.     

Syntheses and structures of nine-coordinate K3[DyIII(nta)2(H2O)]·5H2O and eight-coordinate (NH4)3[DyIII(nta)2] complexes

K₃[Dy^III(nta)₂(H₂O)]·5H₂O and (NH₄)₃[Dy^III(nta)₂] have been synthesized in aqueous solution and characterized by IR, elemental analysis and single-crystal X-ray diffraction techniques. In K₃[Dy^III(nta)₂(H₂O)]·5H₂O the Dy^III ion is nine coordinated yielding a tricapped trigonal prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 15.373(5) Å, b = 12.896(4) Å, c = 26.202(9) Å; β = 96.122(5)°, V = 5165(3) ų, Z = 8, D _c = 1.965 g·cm^?3, μ = 3.458 mm^?1, F(000) = 3016, R ₁ = 0.0452 and wR ₂ = 0.1025 for 4550 observed reflections with I ≥ 2σ(I). In (NH₄)₃[Dy^III(nta)₂] the Dy^III ion is eight coordinated yielding a usual dicapped trigonal anti-prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 13.736(3) Å, b = 7.9389(16) Å, c = 18.781(4) Å; β = 104.099(3)°, V = 1986.3(7) ų, Z = 2, D _c = 1.983 g·cm^?3, μ = 3.834 mm^?1, F(000) = 1172, R ₁ = 0.0208 and wR ₂ = 0.0500 for 2022 observed reflections with I ≥ 2σ(I). The results indicate that the difference in counter ion also influences coordination numbers and structures of rare earth metal complexes with aminopolycarboxylic acid ligands.     

Coordination compounds of cobalt(II) and cadmium(II) with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

The coordination compounds [CoL₂Cl₂] (I) and [CdL₂(H₂O)₂(NO₃)₂] (II) have been synthesized by the reaction of CoCl₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) ų, ρ_calcd = 1.567 g/cm³, Z = 2. The crystals of complex II are monoclinic, space group P2₁/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) ų, ρ_calcd = 1.760 g/cm³, Z = 2. Discrete [CoL₂Cl₂] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-N_avg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd²⁺ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO₃) and O(H₂O) oxygen atoms. The coordination of the Cd²⁺ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO₃ groups.     

Synthesis and structural characterization of a polar Os(II,III) complex,Os2(fhp)4Cl

The title compound was prepared by prolonged reaction of Os₂(CH₃COO)₄Cl₂ with Hfhp (Hfhp = 6-fluoro-2-hydroxypyridine) in refluxing toluene in the presence of LiCl. The product, Os₂(fhp)₄Cl (1), is a result of ligand displacement with a concomitant core reduction of Os₂⁶⁺ to Os₂⁵⁺. Crystals were grown by slow diffusion of hexane into a dichloromethane solution of 1. Crystallographic data are as follows: tetragonal crystal system, space group I4mm (No. 107), a = b = 11.000(3) Å, c = 13.142(2) Å, V= 1590(1) ų, Z = 2. The molecule possesses crystallographic 4mm symmetry, with the OsOs bonds lying along the four-fold axes. The four fhp ligands are arranged in a polar fashion around the diosmium core, blocking one axial site. The second axial position is occupied by a chloride ion. The principal distances in 1 are: Os(1)Os(2) = 2.341(1) Å, Os(1)N = 2.027(12) Å, Os(2)O = 2.014(5) Å, Os(2)Cl = 2.487(7) Å. The title compound was also investigated by several physical methods. The electrochemistry as determined by cyclic voltammetry revealed two processes: a reversible, one-electron reduction at E_ox = −0.63 V in dichloromethane and an irreversible oxidation at E_ox = +0.95 V in dichloromethane vs Ag-AgCl at room temperature. The electronic spectrum shows strong bands at 413 nm (ε = 4290 M⁻¹ cm⁻¹), 309 nm (ε = 23,560 M⁻¹ cm⁻¹) and at 294 nm (ε = 26,500 M⁻¹ cm⁻¹) as well as shoulders at 334 and 261 nm.     

The synthesis and crystal structure of a trinuclear molybdenum cluster compound [Mo3(μ-O)(μ-S)3(μ(μ-OAc)2(dtp)2·(Py)]·0.5H2O

[Mo₃,OS₃(dtp)₄(H₂O)] reacts with NaOAc·3H₂O in Py to give the title compound. The crystal data are as follows: [Mo₂OS₃)(OAc)₂(dtp)₂·Py]?0.5H,O(dtp = [S₃P(OC₂H₅)₂]^?, Py = C₅H₅N); M = 976.64; triclinic; space group P1 ; a=11.704(5), b=14.169(7), c= 11.688 (5) Å α=109.94(4) β = 91.53(4), γ = 91.93(4)°; V= 1819(1) Ų; Z=2; D_c = 1.78 g·cm^?3 λ(Mo Kα) = 0.71069 Å μ=15.15 cm^?1; F(000) = 970 T=296 K; final R=0.071 for 1652 reflections with I>3σ(I). In the molecule, the [Mo₃OS₃] core is surrounded by two bridging OAc groups and two terminal chelate dtp groups attached to the {Mo₃} triangle in a symmetric style, and the Py ligand is coordinated to the Mo atom at the apex of {Mo₃} triangle with the nitrogen. This novel configuration is obtained for the first time with Mo—N bond length being 2.27 (2) Å and three Mo—Mo bond lengths 2.584 (4), 2.587 (4) and 2.657(4) Å, respectively. As a whole, the molecule has a virtual C₂ symmetry.     

Synthesis,crystal structure,and luminescent properties of a new modification of the zinc(II) dichloride complex with phthalazine

The coordination compound [ZnCl₂(Phtz)₂] has been synthesized by the reaction of ZnCl₂ with phthalazine (Phtz, L, C₈H₆N₂) in an ethanol solution. Its crystal structure has been determined: crystals are triclinic, space group P 0000000, a = 7.346(1) Å, b = 8.095(1) Å, c = 14.275(1) Å, α = 85.63(1)°, β = 75.75(1)°, γ = 88.43(1)°, V = 820.4(2) ų, ρ_calc = 1.605 g/cm³, Z = 2. The zinc atom is tetrahedrally coordinated to two crystallographically nonequivalent chlorine atoms and two nitrogen atoms of the ligands L (Zn(1)–N(1), 2.036(4) Å; Zn(1)–N(3), 2.043(4) Å; Zn(1)–Cl(1), 2.225(2) Å; Zn(1)–Cl(2), 2.220(2) Å; angles NZnN, 106.1(2)°; ClZnCl, 116.47(7)°). The complexes are combined into a 1D supramolecular structure by nonclassical hydrogen bonds C–H···Cl and π–π-stacking interaction between centrosymmetric pairs of aromatic rings of one of the independent ligands. The compounds [CdI₂(Phtz)] and [HgBr₂(Phtz)] have also been synthesized, and their luminescent properties have been studied.     

Synthetic and structural chemistry of nickel(II) complexes containing dithiolato and phosphine ligands I. Preparation and crystal structure of Ni2(PPh3)2(edt)2

A nickel(II) complex containing both dithiolato and phosphine ligands, Ni₂(PPh₃)₂(edt)₂ (edt = SCH₂CH₂S^2-), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3) Å, α = 102.84(2), β = 96.49 (2), γ = 82.56(3); V = 1906.8 ų; D_c = 1.439 g·cm^?3 for Z = 2; the final conventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni—Ni distance of 2.893 Å, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average length of Ni—S bond is 2.180 Å and Ni—P bond 2.188 Å. The UV-Vis and ¹H NMR spectra have also been recorded.     

The crystal and molecular structure of ortho-terphenylenemercury dimer, (C18H12Hg)2

C₃₆H₂₄Hg₂, hexabenzo[b,d,f,i,k,m][1,8] dimercuracyclotetradecene, M_r = 857.768, monoclinic, P2₁/n, a 17.315(3), b 16.576(2), c 10.545(6) Å, β 114.60(4)°, U 2751.65 ų, Z = 4, D_m 2.055, D_x 2.071 g cm⁻³, λ(Mo-K_α) 0.71069 Å, μ 107.51 cm⁻¹, F(000) = 1600, T 293 K; Final R = 0.041 for 4290 observed reflections with I > 3σ(I). The two CHgC angles are 175.5(3) and 175.6(4)°; average CHg distance, 2.088(13) Å.     

A density functional study of Fe(SINGLE BOND)N2, Fe(SINGLE BOND)N+2, and Fe(SINGLE BOND)N−2

The interaction of an iron atom with molecular nitrogen was studied using density functional theory. Calculations were of the all-electron type and both conventional local and gradient-dependent models were used. A ground state of linear structure was found for Fe(SINGLE BOND)N₂, with 2S + 1 = 3, whereas the triangular Fe(SINGLE BOND)N₂ geometry, of C_2v symmetry, was located 2.1 kcal/mol higher in energy, at least for the gradient-dependent model. The reversed order was found using the conventional local approximation. In Fe(SINGLE BOND)N₂, the N(SINGLE BOND)N bond is strongly perturbed by the iron atom: It has a bond order of 2.4, a vibrational frequency of 1886 cm⁻¹, and an equilibrium bond length of 1.16 Å: These values are 3.0, 2359 cm⁻¹, and 1.095 Å, respectively, for the free N₂ molecule. With the gradient-dependent model and corrections for nonsphericity of the Fe atom, a very small binding energy, 8.8 kcal/mol, was calculated for Fe(SINGLE BOND)N₂. Quartet ground states were found for both Fe(SINGLE BOND)N⁺₂ and Fe(SINGLE BOND)N⁻₂. The adiabatic ionization potential, electron affinity, and electronegativity were also computed; the predicted values are 7.2, 1.22, and 4.2 eV, respectively. © 1997 John Wiley & Sons, Inc.     

The chemistry and the stereochemistry of poly(n-alkyliminoalanes) : III. The crystal and molecular structure of the adduct (HalN-i-Pr)6AlH3

The crystal and molecular structure of the adduct (HAlN-i-Pr)₆AlH₃ has been determined from single-crystal and three dimensional X-ray diffraction data collected by counter methods. The cage-type molecular structure consists of two six-membered rings, (AlN)₃, joined together by four adjacent transverse AlN bonds; the loss of two of these bonds allows the complexation of one alane molecule, with five-coordination of the aluminum (trigonal bipyramidal geometry), through two AlN bonds and two AlHAl bridge bonds. The AlN bond lengths range from 1.873 to 1.959 Å; the average AlH bond length is 1.50(1) Å for the four-coordinated aluminum atoms; the average distance of the two apical hydrogens from the five-coordinated aluminum atom is 1.92(5) Å. Colourless prismatic crystals of the compound have the following crystal data: triclinic space group P$\text{1}$; a = 17.13(2); b = 10.78(2); c = 10.20(2) Å; α = 124.3(4), β = 92.0(4), γ = 92.1(5); Z = 2; calculated density 1.157 g/cm³. The structure has been refined by block-matrix, least-squares methods using 4358 independent reflections to a standard unweighted R factor of 4.9%.     

Die molekül- und kristallstruktur von thallium-tris(bistrimethylsilylamin), Tl[N(SiMe3)2]3

The molecular and crystal structure of tris(bistrimethylsilylamin)thallium was determined by means of single-crystal X-ray spectroscopy: in the space group P$\text{3}$1c with a = 16.447(7), c = 8.456(7) Å; and D_c = 1.149 g cm^?3 two molecules are located in the unit cell. The compound is isomorphous to the analogues Fe[N(SiMe₃)₂]₃ or Al[N(SiMe₃)₂]₃, respectively, which show a propellar-twist of the Si₂N-groups versus the plane of the metal atom and the three nitrogen-atoms: Tl(N)₃/Si₂N 49.1°; SiNSi 122.6°; NSiC 111.8°; CSiC 107.1°; TlN 2.089 Å;; SiN 1.738 Å;; $\text{SiC}$ 1.889 Å;.     

Copper(I) and silver(I) complexes of 2-amino-1,3,4-thiadiazole and 2-ethylamino-1,3,4-thiadiazole

The following copper(I) and silver(I) complexes of 2-amino-1,3,4-thiadiazole (atz) and 2-ethylamino-1,3,4-thiadiazole (eatz) have been prepared and studied by conductometric, IR and Raman methods: CuXL(X = Cl, Br, I; L = atz, eatz), CuXL₃(X = ClO₄, NO₃; L = atz, eatz), AgClO₄·1.5atz·1/3 EtOH, AgNO₃·2.5atz, AgClO₄·3eatz, AgNO₃·eatz. The ligands are bonded through the amine nitrogen atoms with ν(MN) bands in the 520–410 cm^?1 region. The CuXL complexes have a trigonal (N, 2X_b) coordination with a probable weaker axial interaction. The CuXL₃ and AgCIO₄·3eatz complexes probably have a trigonal pyramidal (3N,O) coordination. In the atz complexes of silver perchlorate and nitrate some ligand molecules are bridging. The AgNO₃·2.5atz complex is likely to have a dimeric structure with tetrahedral coordination of the silver ion.     

The interaction of aromatic hydrocarbons with organometallic compounds of the main group elements : III. The crystal structure of K[Al2(CH3)6F]·C6H6

The crystal structure of K[Al₂(CH₃)₆F]·C₆H₆ has been determined from three-dimensional X-ray data measured by counter methods. The compound crystallizes in the orthorhombic space group Pnma with cell dimensions a = 14.071(5), b = 14.404(5), c = 8.862(3) Å and ρ_calc = 1.04 g·cm^-3 for Z = 4. Least squares refinement gave a conventional weighted R factor of 0.037 for 973 independent observed reflections. In the fluorine-bridged anion, the aluminum—fluorine—aluminum bond angle is fixed at 180° by crystallographic symmetry. The aluminum—fluorine bond length of 1.782(2) Å is compared to other halogen-bridged systems. The potassium ion coordination sphere contains six methyl groups at distances from 3.23 to 3.47 Å; the benzene functions as a molecule of crystallization with 3.947(7) Å as the shortest benzene carbon—potassium ion approach.     

Synthesis and crystal structure of mixed-cation salt of trans-hydroxotetranitronitrosoruthenium(II) complex, KNa[Ru(NO)(NO2)4(OH)]·H2O

The mixed-cation complex salt KNa[Ru(NO)(NO₂)₄(OH)]·H₂O has been synthesized and studied with methods of IR-spectroscopy, X-ray phase and X-ray structural analysis. The crystallographic data for H₃KN₅NaO₁₁Ru are: a = 7.389(1) Å, b = 14.196(2) Å, c = 21.507(5) Å; V = 2256.0(7) ų, Z = 8, d _calc = 2.427 g/cm³, space group is P2₁2₁2₁. The structure is chiral and its absolute structural parameter equals 0.04. General motif of the arrangement of complex anions was determined by the translation sublattice method. Geometric characteristics for coordinate NO₂-groups in structurally characterized nitro complexes of ruthenium(II) have been analyzed.     

Copper(II)-assisted thorough hydrolysis of 2,4,6-tris(2-pyridyl)1,3,5-triazine (tptz). Crystal structures of bis(2-pyridylcarboxylato)-copper(II) dihydrate and bis(2-pyridylcarbonyl)-amido-2,4,6-tris(2-pyridyl)-1,3,5-triazine-copper(II) dicyanamide heptahydrate

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz) undergoes hydrolysis in the presence of copper(II) acetate affording bis(2-pyridylcarbonyl)amido-copper(II) and free 2-pyridylcarboxylic anion. Two compounds of formulas [Cu(NC₅H₄COO)₂]·2H₂O (1) and [Cu(NC₅H₄CO)₂N(tptz)](N(CN)₂)·7H₂O (2), where NC₅H₄COO^? and (NC₅H₄CO)₂N^? are 2-pyridylcarboxylate and bis(2-pyridylcarbonyl)amido-anion, respectively, were obtained from methanol/ethanol solution of tptz with copper acetate; they were characterized by element analysis and single crystal X-ray diffraction method. Single crystal XRD analysis shows that in complex 1 coordination number around Cu atom is 4 with distorted square-planar coordination geometry and in complex 2 coordination number around Cu atom is 6 with distorted octahedral geometry. Crystal data for 1: a = 5.1359(10) Å, b = 7.6471(15) Å, c = 9.2303(18) Å, α = 74.90(3)°, β = 84.36(3)°, γ = 71.37(3)°, space group P1, crystal system triclinic, Z = 1, V = 331.6(1) ų, d _calc = 1.721 g/cm³. Crystallographic data for 2: space group C2/c, crystal system monoclinic, a = 23.976(5) Å, b = 15.465(3) Å, c = 18.649(4) Å, β = 92.66(3)°, V = 6907(2) ų, d _calc = 1.0448 g/cm³, Z = 4.     

A novel three-dimensional cobalt(II)-radical complex Co(NITmPy)2[N(CN)2]2: Structure and magnetic properties

A novel three-dimensional cobalt(II)-radical complex {Co(NITmPy)₂[N(CN)₂]₂}_n (NITmPy = 2-(3′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) is prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic system, space group P2₁/c, with unit cell parameters a = 12.5775(5) Å, b = 10.9340(5) Å, c = 11.6134(5) Å, β = 108.1320(10)°; V = 1517.79(11) ų, ρ_calcd = 1.443 g/cm³, and Z = 2 for R ₁ = 0.0463. In the complex, each cobalt ion is six-coordinate with four nitrogen atoms from four N(CN) ₂ ^t- ligands and two nitrogen atoms of pyridyl groups, and the [Co(NITmPy)₂]²⁺ units are linked by N(CN) ₂ ^t- μ-bridging ligands to form a three-dimensional structure. The variable-temperature magnetic susceptibility data show that the complex exhibits weak antiferromagnetic interactions.     

Synthesis and molecular structure of the polar,binuclear complex,monochlorotetra-(6-fluoro-2-oxopyridine)diruthenium(II,III)

The dark purple title compound was prepared by reaction of Ru₂Cl(O₂CCH₃)₄ with molten 6-fluoro-2-hydroxypyrine (Hfhp) in quantitative yield. Crystals of composition Ru₂Cl(fhp)₄ were obtained by slow diffusion of hexane into a CH₂Cl₂ solution of the compound. The crystals belong to the tetragonal space group I4mm with the following unit-cell dimensions: a = b = 10.890(2) Å, c = 13.178(4) Å, α = β = γ = 90.0°, V = 1562.8(6) ų, and Z = 2. The Ru₂Cl(fhp)₄ molecule, which has crystallographic 4mm (C_4c) symmetry, contains a diruthenium(II,III) unit with a metalmetal bond order of 2.5. The four bridging fhp ligands across the Ru₂ unit are oriented in one direction to form a polar molecule. The coordinatioin spheres of the two ruthenium atoms [Ru(1) and Ru(2)] are Ru(2)N(I)₄ and Ru(1)Cl(1)O(1)₄, respectively. The axial site on Ru(1) is blocked by four F(1) atoms. The Ru(1)Ru(2), Ru(2)Cl(1), Ru(2)O(1) and Ru(1)N(1) distances are 2.284(1), 2.427(3), 1.971(2) and 2.089(4) Å, respectively. The electronic spectrum of the compound in CH₂Cl₂ shows two strong bands at 552 nm (ε = 4720 M⁻¹ cm⁻¹) and 355 nm ε = 3770 M⁻¹ cm⁻¹). Cyclic voltammetry of Ru₂Cl(fhp)₄ in CH₂Cl₂ in the presence of 0.1 M [N(C₂H₅)₄]ClO₄ at 100 mV s⁻¹ shows two quasireversible metal-centered one-electron oxication and reduction processes at +1.68 (ΔE_p = 120 mV) and −0.01 V (ΔE_p = 126 mV), respectively, vs an AgAgCl reference electrode.     

trans-Bis(triphenylphosphin)phthalocyaninato(2–)rhenium(II): Synthese,Eigenschaften und Kristallstruktur

trans -Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II): Synthesis, Properties, and Crystal Structure Dirheniumheptoxide reacts with phthalodinitrile in boiling 1-chloronaphthalene and subsequent reprecipitation of the green raw product from conc. sulfuric acid to yield an oxo-phthalocyaninate of rhenium, which is reduced by molten triphenylphosphine forming dark green trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), ^trans[Re(PPh₃)₂pc^2–]. The latter crystallizes triclinic in the space group P 1 with the cell parameters as follows: a = 11.512(2) Å, b = 12.795(2) Å, c = 12.858(2) Å, α = 64.42(2)°, β = 79.45(2)°, γ = 72.74(1)°; V = 1628.1(5); Z = 1. Re is in the centre of the (N_p)₄ plane (N_p: N1, N3) and coordinates two triphenylphosphine ligands axially in trans position. The average Re–N_p and Re–P distances are 2.007(1) and 2.516(3) Å, respectively. Despite the many extra bands the typical B, Q and N regions of the pc^2– ligand are observed at ca. 16500, 28900/32900 and 35300 cm^–1. A weak band group at ca. 8900 cm^–1 is attributed to a trip-multiplet transition, another one at ca. 14500 cm^–1 to a P → Re charge transfer. The vibrational spectra are dominated by internal vibrations of the pc^2– ligand. The very weak intensity of the IR bands at 905 and 1327 cm^–1 are diagnostic of the presence of Re^II.