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1.
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)2pc2–]. 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 (Np)4 plane (Np: N1, N3) and coordinates two triphenylphosphine ligands axially in trans position. The average Re–Np 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 pc2– 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 pc2– ligand. The very weak intensity of the IR bands at 905 and 1327 cm–1 are diagnostic of the presence of ReII. 相似文献
2.
Bis(triphenylphosphine)iminium Bis(methoxo)phthalocyaninato(2–)ferrate(III) – Synthesis and Crystal Structure Chlorophthalocyaninato(2–)ferrate(III) reacts with bis(triphenylphosphine)iminium hydroxide in methanol/acetone solution to yield blue crystals of bis(triphenylphosphine)iminium bis(methoxo)phthalocyaninato(2–)ferrate(III). The complex salt crystallizes as an acetone/methanol solvate (bPNP)[Fe(OCH3)2pc2–] · (CH3)2CO · 1.5 CH3OH in the triclinic space group P 1 (no. 2) with the cell parameters a = 13.160(5) Å, b = 15.480(5) Å, c = 17.140(5) Å, α = 97.54(5)°, β = 91.79(5)°, γ = 95.44(5)°. The Fe atom is located in the centre of the pc2– ligand coordinating four isoindole N atoms (Niso) of the pc2– ligand and two O atoms of the methoxo ligands in a mutual trans arrangement. The average Fe–O and Fe–Niso distances are 1.887 and 1.943 Å, respectively. The cation adopts the bent conformation (< P–N–P = 140.4(2)°) with P–N distances of 1.579(3) and 1.575(3) Å. 相似文献
3.
Melanie Gldner Brbel Geniffke Andreas Franken Keith S. Murray Heiner Homborg 《无机化学与普通化学杂志》2001,627(5):935-947
Mononitrosyl and trans ‐Dinitrosyl Complexes of Phthalocyaninates of Manganese and Rhenium Tetra(n‐butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthalocyaninato(2–)manganate, (cat)[Mn(NO)(X)pc2–] (X = ONO, NCO, N3; cat = nBu4N, PNP) is prepared from acidophthalocyaninato(2–)manganese, [Mn(X)pc2–], (cat)NO2 and (nBu4N)BH4 in CH2Cl2 or from nitrosylphthalocyaninato(2–)manganese, [Mn(NO)pc2–] and (nBu4N)X (X = ONO, NCO, N3, NCS) at T < 120 °C, respectively. [Mn(NO)(X)pc2–]– dissociates in methanol, and [Mn(NO)pc2–] precipitates. Nitrito(O)phthalocyaninato(2–)manganese, (cat)NO2 and hydrogensulfide yield trans‐di(nitrosyl)phthalocyaninato(2–)manganate, trans[Mn(NO)2pc2–]–, isolated as red violet (PNP) and (nBu4N) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)manganese, [Mn(NO)(OPPh3)pc2–] is obtained by addition of OPPh3 to [Mn(NO)pc2–] at 200 °C. Di(triphenylphosphane)phthalocyaninato(2–)rhenium(II) and (PNP)NO2 in CH2Cl2 or in molten (PNP)NO2 and PPh3 at 100 °C yields green blue l‐di(triphenylphosphane)iminium nitrosylnitrito(O)phthalocyaninato(2–)rhenate, l(PNP)[Re(NO)(ONO)pc2–]. Similarly, but with (nBu4N)NO2 red plates of tetra‐(n‐butyl)ammonium trans‐di(nitrosyl)phthalocyaninato(2–)rhenate, (nBu4N)trans[Re(NO)2pc2–] is isolated. Addition of (PNP)Br or (PNP)PF6 to a concentrated solution of (nBu4N)trans[Re(NO)2pc2–] in pyridine precipitates l(PNP)trans[Re(NO)2pc2–]. (nBu4N)trans[Re(NO)2pc2–] and PPh3 at 300 °C yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)‐ rhenium, [Re(NO)(OPPh3)pc2–], that is oxidised with iodine precipitating nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)rhenium triiodide, [Re(NO)(OPPh3)pc2–]I3. The crystal structures of l(PNP)[Mn(NO)(ONO)pc2–] ( 1 ), l(PNP)‐ [Mn(NO)(NCO)pc2–] ( 2 ), l(PNP)trans[Mn(NO)2pc2–] ( 3 ), l(PNP)trans[Re(NO)2pc2–] ( 4 ) [Mn(NO)(OPPh3)pc2–] ( 5 ), [Re(NO)(OPPh3)pc2–] ( 6 ), and [Re(NO)(OPPh3)pc2–]I3 · CH2Cl2 ( 7 ) have been determined. The M–N(NO) distance varies between 1.623(12) Å in 5 and 1.846(3) Å in 3 . The M–N–O moiety is almost linear. The UV‐Vis spectra with the B band at ca. 14500 cm–1and the Q band at 30400 cm–1 do not dependent significantly on the axial ligand and the metal atom and its oxidation state. N–O stretching vibrations are observed in the IR spectra between 1701 cm–1 in 3 and 1753 cm–1 in [Mn(NO)pc2–] or for the Re series between 1571 cm–1 in 4 and 1724 cm–1 in 7 . M–N(NO) stretching and M–N–O deformation vibrations are assigned in the IR spectra and resonance Raman spectra between 486 cm–1 in 4 and 620 cm–1 in 1 . 相似文献
4.
Oxophthalocyaninato(2–)molybdenum(IV), activated by bromine oxidation prior to use, reacts with fused triphenylphosphine in the presence of bis(triphenylphosphine)iminium bromide to yield linear-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2–)molybdate(III), l(PNP)trans[Mo(Br)2pc2?]. It crystallizes triclinic with crystal data: a = 10.506(1) Å, b = 12.436(2) Å, c = 12.918(2) Å, α = 76.186(1)°, β = 67.890(1)°, γ = 68.689(1)°; space group P1 (No. 2); Z = 1. MoIII is in a pseudo-octahedral coordination geometry with the bromo ligands in trans-arrangement. The Mo? Np and Mo? Br distance is 2.043(10) and 2.588(1) Å, respectively. The PNP cation adopts a linear conformation. In the IR spectrum vas(Mo? Br) is observed at 218 cm?1 and vas(P? N) of the linear (P? N? P) core at 1406 cm?1. Cyclic and differential-pulse voltammetry show two quasi-reversible cathodic processes at ?1.15 and ?0.53 V vs. Ag/AgCl. The first is assigned to a phthalocyaninate directed reduction (pc2?/pc3?), while the latter arises from a Mo directed reduction (MoIII/MoII). Spectral monitoring confirms the reversible MoIII/MoII reduction. Two quasi-reversible anodic processes at 0.60 and 1.27 V are assigned to the successive Mo directed oxidation with redox couples MoIII/MoIV and MoIV/MoV. For the first time, three very intense spin-allowed trip-quartet transitions are observed in the electronic absorption spectra at 7140 (TQI), 16890 (TQ2) and 18700 cm?1 (TQ3) together with a sing-quartet transition at 15850 cm?1 and characteristic ?Q”? region with maximum at 28500 cm?1 and ?N”? region at 37400 cm?1. All electronic excitations are of comparable intensity. A prominent low temperature emission at 6690 cm?1 is assigned to a spin-forbidden trip-sextet. 相似文献
5.
Crystal Structure, Vibrational Spectrum, and Normal Coordinate Analysis of (PNP)2[ReFBr5] · H2O From the complex mixture obtained by oxidative ligand exchange of [ReBr6]2– with BrF3 [ReFBr5]2– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose with 45% yield. The X-ray structure determination of (PNP)2[ReFBr5] · H2O (monoclinic, space group P21/c with a = 21.498(2), b = 13.314(3), c = 23.945(2) Å, β = 105.235(7)°, Z = 4) reveals a completely ordered anion sublattice resulting from the solvent water linked to the F ligand by a hydrogen bond (O–F: 2.758(6) Å). Due to the stronger trans influence of Br compared with F on the F · –Re–Br′ axis the Re–Br′ distance is shortened by 0.6% with regard to symmetrically coordinated axes. Based on the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectrum of the (Me4N) salt is assigned by a normal coordinate analysis. The strengthening of the Re–Br′ bond due to the trans influence is indicated by an increase of the valence force constant fd(ReBr′) = 1.43 by 8% as compared with fd(ReBr) = 1.32 mdyn/Å of symmetric axes. 相似文献
6.
Melanie Gldner Heiner Hückstdt Keith S. Murray Boujemaa Moubaraki Heiner Homborg 《无机化学与普通化学杂志》1998,624(2):288-294
Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μeff = 0,88 μB, per Re, at 300 K) is prepared by thermal decomposition of trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (Niso)4 planes by 0.426(3) Å. The Re–Niso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc2– ligands are in an eclipsed conformation and concavely distorted. In the UV-VIS-NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm–1 is selectively enhanced in the resonance Raman spectrum (λexc = 488 nm). 相似文献
7.
CrIII Phthalocyaninates: Synthesis, Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Di(nitrito(O))phthalocyaninato(2–)chromate(III) [Cr(H2O)2Pc2?]Ix reacts with excess (PNP)NO2 in dimethylformamide to yield less soluble greenblack l-bis(triphenylphosphine)iminium trans-di(nitrito(O))phthalocyaninato(2–)chromate(III), l(PNP)trans[Cr(ONO)2Pc2?], which crystallizes in the triclinic space group P1 (No. 2) with Z = 2. The Cr atom is in the center of the Pc2? ligand and the two nitrite ions are monodentate O-coordinated in a mutually trans arrangement to the Cr atom. The Cr? O and Cr? Niso bond distances are 1.9898(14) und 1.981(2) Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.307(2) Å; d(N? O) = 1.205(2) Å; ?(O? N? O) = 113.7(2)°; ?(Cr? O? N) = 116.85(12)°. The non-bonding O atoms are trans to the Cr atom. The Pc2? ligand is slightly saddled. Three weak spin-allowed trip-quartet(TQ) transitions (in 103 cm?1): TQ1 (8.20) < TQ2 (11.3) < TQ3 (20.33) and the characteristic π-π* transitions of the Pc2? ligand: B (14.68) < Q1 (27.1) < Q2 (29.0) < N (35.4) are observed in the UV-VIS-NIR spectrum. Prominent luminescence spectra are obtained by excitation within the TQ1 region, in which the spin-forbidden trip-sextet transition at 7376 cm?1 dominates at low temperatures (T < 50 K). The vibrational spectra are discussed. In coincidence of the excitation lines with TQ3, vs(Cr? O) at 378 cm?1 is selectively resonance Raman (RR) enhanced. vas(Cr? O) is observed in the FIR spectrum at 391 cm?1. The following internal vibrations (in cm?1) of the nitrito ligand are in the MIR spectrum: vas(N? O)/1447 > vas(N? O)/1018/1029 > δ(O? N? O)/828 and in the RR-spectrum: vs(N? O)/1410 > vs(N? O)/952, the last followed by three overtones. 相似文献
8.
Preparation and Properties of Tetra(n-butyl)ammonium cis -Trifluorophthalocyaninato(2–)zirconate(IV) and -hafnate(IV); Crystal Structure of (nBu4N) cis [Hf(F)3pc2–] cis-Dichlorophthalocyaninato(2–)metal(IV) of zirconium and hafnium reacts with excess tetra(n-butyl)-ammoniumfluoride trihydrate to yield tetra(n-butyl)-ammonium cis-trifluorophthalocyaninato(2–)metalate(IV), (nBu4N)cis[M(F)3pc2–] (M = Zr, Hf). (nBu4N)cis[Hf(F)3pc2–] crystallizes in the monoclinic space group P21/n (# 14) with cell parameters a = 13.517(1) Å, b = 13.856(1) Å, c = 23.384(2) Å, α = 92.67(1)°, Z = 4. The Hf atom is in a ”︁square base-trigonal cap”︁”︁ polyhedron, coordinating three fluorine atoms and four isoindole nitrogen atoms (Niso). The Hf atom is sandwiched between the (Niso)4 and F3 planes (d(Hf–CtN) = 1.218(3) Å; d(Hf–CtF) = 1.229(3) Å; CtN/F: centre of the (Niso)4, respectively F3 plane). The average Hf–Niso and Hf–F distances are 2.298 and 1.964 Å, respectively, the average F–Hf–F angle is 84.9°. The pc2– ligand is concavely distorted. The optical spectra show the typical metal independent π-π* transitions of the pc2– ligand at c. 14700 and 29000 cm–1. In the FIR/MIR spectra vibrations of the MF3 skeleton are detected at 545, 489, 274 cm–1 (M = Zr) and 536, 484, 263 cm–1 (M = Hf), respectively. 相似文献
9.
Bis(bis(triphenylphosphine)iminium) μ-Nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) Triiodide Diethylether Di-Solvate: Synthesis, Properties, and Crystal Structure Bis(bis(triphenylphosphine)iminium) μ-nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) triiodide is prepared as a diethylether di-solvate by substitution of μ-nitrido-bis(pyridinephthalocyaninato(2–)iron(IV)) pentaiodide with bis(triphenylphosphine)iminium azide in acetone and precipitation by slow diffusion of diethylether. The doublesalt crystallizes monoclinically in the space group C12/c1 with cell parameters: a = 34.567(9) Å, b = 20.237(9) Å, c = 21.251(5) Å, β = 119.79(2)°; Z = 4. The Fe atoms are located almost in the centre (Ct) of the (Niso)4 planes (d(Fe–Ct) = 0.080(1) Å; Niso: isoindoline N atom). The average Fe–Niso distance is 1.947(5) Å, the Fe-(μ-N) distance 1.650(1) Å. The Fe-(μ-N)–Fe skeleton is linear (177.4(4)°). Both waving pc2– ligands are in a staggered conformation (skew angle φ = 38.5(5)°). Fe coordinates linear azide (d(Fe–Nazide) = 2.152(7) Å) with an angle of 121.2(6)°. The isolated triiodide ion is almost linear (d(I–I) = 2.936(2) Å). The PNP cation obtains an hybrid conformation (∠(P–N–P) = 157.4(2)°). The asymmetrical Fe-(μ-N)–Fe stretching vibration is observed in the IR spectrum at 997 cm–1, the symmetrical one is selectively enhanced in the resonance Raman (RR) spectrum at 478 cm–1. The corresponding I–I stretching vibrations of the triiodide ion are present in the actual spectra at 134 (IR) and 115 cm–1 (RR). An IR band at 334 cm–1 is attributed to the asymmetrical Fe–Nazide stretching vibration. 相似文献
10.
Preparation and Properties of Phthalocyaninato(2–)indates(III) with Monodentate Acido Ligands; Crystal Structure of Tetra(n-butyl)ammonium cis -Difluorophthalocyaninato(2–)indate(III) Hydrate Tetra(n-butyl)ammonium cis-diacidophthalocyaninato(2–)indates(III) with the monodentate acido ligands fluoride, chloride, cyanide and formiate are synthezised by the reaction of chlorophthalocyaninatoindium(III) or cis-dihydroxophthalocyaninatoindate(III) with the respective tetra(n-butyl)ammonium salt or ammonium formiate and are characterized by their UV/VIS spectra and their vibrational spectra. The difluoro-complex salt crystallizes as a hydrate ((nBu4N)cis[In(F)2pc2–] · H2O) in the monoclinic space group P21/n (no. 14) with cell parameters: a = 13.081(3) Å, b = 13.936(2) Å, c = 23.972(2) Å; β = 97.79(1)°, Z = 4. Hexa-coordinated indium is surrounded by four isoindole nitrogen atoms (Niso) and two cis-positioned fluorine atoms. The average In–F and In–Niso distance are 2.0685(4) and 2.2033(5) Å, respectively, and the F–In–F angle is 81.5(1)°. The In atom is displaced outside the centre (Ct) of the Niso plane towards the fluoride ligands: d(In–Ct) = 0.953(1) Å. The phthalocyaninato(2–) core is nonplanar (unsymmetrical concave distortion). 相似文献
11.
Syntheses and Properties of (Acido)(pyridine)phthalocyaninato(2–)ruthenates(II); Crystal Structure of Tetra(n-butyl)ammonium (Cyano)(pyridine)phthalocyaninato(2–)ruthenate(II) Bis(tetra(n-butyl)ammonium bis(acido)phthalocyaninato(2–)ruthenate(II) reacts in boiling pyridine to yield blue purple, diamagnetic tetra(n-butyl)ammonium (acido)(pyridine)phthalocyaninato(2–)ruthenate(II), (nBu4N)[Ru(X)(py)pc2–] (X = CN, N3, NCS, NCO, NO2). (nBu4N)[Ru(CN)(py)pc2–] crystallizes in the orthorhombic space group Pca21 (no. 29) with cell parameters a = 28.319(5) Å, b = 29.850(3) Å, c = 24.566(7) Å, Z = 16, with four crystallographically independent complex anions present in the unit cell. Each Ru atom is located outside the centre (Ct) of the corresponding (Niso)4 plane (Niso: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (Niso)4 plane towards cyanide (d(Ru–Ct)) is 0.020 Å. The Ru–Niso distance varies from 1.947(2) to 1.992(2) Å. The average Ru–C and Ru–Npy distance is 2.00 Å and 2.19 Å, respectively. The pc2– ligand ist slightly distorted towards the cyanide. The cyclic and differential pulse voltammograms of (nBu4N)[Ru(X)(py)pc2–] exhibit the first quasi-reversible one electron process (in V) at 0.46 (X = CN), 0.34 (N3), 0.40 (NCO), 0.47 (NO2), 0.50 V (NCS) and the second, independent of X, at approximately 1.05 V. The first process is metal directed, the second ring directed. The electronic absorption spectra and the vibrational spectra of (nBu4N)[Ru(X)(py)pc2–] are discussed. 相似文献
12.
Syntheses and Properties of Phthalocyaninato(2–)metallates(I) of Cobalt, Rhodium, and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Phthalocyaninato(2–)cobaltate(I) Acetone Solvate Cobaltphthalocyaninate(2–) reacts with tetra(n-butyl)ammonium boranate in acetone yielding soluble tetra(n-butyl)ammonium phthalocyaninato(2–)cobaltate(I). The green platelets of its acetone solvate crystallize in the monoclinic space group P1 21/c (no. 14) with cell parameters: a = 12.370(1) Å, b = 23.370(3) Å, c = 15.952(8) Å, β = 93.55(2)°, Z = 4. The Co atom is located in the centre of the distorted phthalocyaninate (waving distortion). The average Co–Niso distance is 1.894 Å. Dichlorophthalocyaninato(2–)metal(III) acid of rhodium and iridium reacts in boiling sodium isopropylate/isopropanol with tetra(n-butyl)ammonium boranate yielding violet tetra(n-butyl)ammonium phthalocyaninato(2–)rhodate(I) and -iridate(I). The UV-VIS-NIR spectra show normal π–π* transitions of the pc2– ligand which are shifted in the series Co < Rh < Ir to higher energy. Absorbances (in 103 cm–1) at 18.2/19.4/21.4/23.6 (Co), 22.0/22.8/40.4 (Rh) and 25.6 (Ir) are assigned to M → pc2– charge transfer transitions. The vibrational spectra are typical for the pc2– ligand. The very low absorbance of the IR bands at 916/1067/1330 cm–1 is diagnostic for low-valent metal phthalocyaninates. 相似文献
13.
Andreas Tutaß Melanie Gldner Heiner Hückstdt Ursula Cornelissen Heiner Homborg 《无机化学与普通化学杂志》2001,627(10):2323-2336
Mononuclear and Multiply Bridged Dinuclear Phthalocyaninates(1–/2–) of Yttrium by Solvent Controlled Condensation; Small Solvent Clusters as Ligands Green chlorophthalocyaninato(2–)yttrium(III), [Y(Cl)pc2–] forms when yttrium chloride is heated with o‐phthalonitrile in 1‐chloronaphthalene. Black cis‐di(chloro)phthalocyaninato(1‐)yttrium(III), cis[Y(Cl)2pc–] is obtained as a stable intermediate by partial reduction. Both complexes are soluble in many O‐donor solvents and pyridine. The solubility in water is remarkable: [Y(Cl)pc2–] dissolves with green, cis[Y(Cl)2pc–] with red‐violet color. Typical absorptions of the pc2– ligand are observed at 14800 and 29700 cm–1. A solvent dependent monomer‐dimer equilibrium is found for the pc– radical. The monomer with absorptions at 12100 and 19900 cm–1 is favored in non‐polar solvents, while in polar solvents the dimer with absorptions at 8700, 13200 and 18600 cm–1 is preferred. cis‐Tri(dimethylformamide)chlorophthalocyaninato(2–)yttrium(III) etherate ( 1 ) crystallises from a solution of [Y(Cl)pc2–] in MeOH/dmf, cis‐tetra(dimethylsulfoxide)phthalocyaninato(2–)yttrium(III) chloride etherate methanol disolvate ( 2 ) from thf/dmso, μ‐di(chloro)‐μ‐di〈di(pyridine)(μ‐water)〉di(phthalocyaninato(2–)‐ yttrium(III)) ( 5 ) from py, and cis‐(chloro)pyridine(triphenylphosphine oxide)phthalocyaninato(2–)yttrium(III) semi‐etherate ( 3 ) is obtained from a solution of [Y(Cl)pc2–] and triphenylphosphine oxide in py. 1 condenses in MeOH yielding a (1 : 1)‐mixture ( 4 ) of μ‐di(chloro)di(〈trans‐(diwaterdimethanol)〉〈dimethanol〉phthalocyaninato(2–)yttrium(III)) ( 4 a ) and μ‐di(chloro)di(dimethylformamide〈dimethanol〉phthalocyaninato(2–)yttrium(III)) ( 4 b ); co‐ordinatively bound solvent clusters are in brakets. The structures of 1 – 5 have been established by X‐ray crystallography. Apart from 3 with hepta‐co‐ordinated yttrium, the metal ion prefers octa‐co‐ordination, and the bond arrangement around Y3+ is always a distorted quadratic antiprism. In the dinuclear complexes obtained by solvent controlled condensation both antiprisms share an edge by two μ‐Cl atoms in 4 , while in 5 the antiprisms are face‐shared by two trans positioned μ‐Cl atoms and μ‐O atoms, respectively. In 5 , the bent b〈{py}2(μ‐H2O)〉 cluster is stabilised by a combined interplanar bonding of pyridine by short N…H–O bonds (d(N…O) = 2.664(7) Å; 2.81(2) Å) and strong van‐der‐Waals interactions with the ecliptic pc2– ligands. 4 a and 4 b contain the dimeric methanol cluster 〈(MeOH)2〉, and 4 a in addition the cyclic heterotetrameric trans‐diwaterdimethanol cluster, transc〈(H2O)2(MeOH)2〉. The neutral clusters co‐ordinatively bound to the Y atom are compared with structurally established cluster‐anions of type 〈(OMe)(MeOH)〉–, linear l〈(OMe)(MeOH)2〉–, cyclic c〈(OH)3(H2O)3〉3–, b〈{H2O}2(μ‐O)〉2–, and b{H2O}2(μ‐F)〉–. 相似文献
14.
Zirconiumphthalocyanines: Synthesis and Properties of Chloride Ligated Phthalocyanines of Ter- and Quadrivalent Zirconium; Crystal Structure of cis-Di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2–)zirconate(IV)-di(dichloromethane) cis-Di(chloro)phthalocyaninato(2–)zirconium(IV) is obtained by the reaction of ZrCl4 with phthalodinitrile in 1-chloronaphthaline at 230°C. It reacts with molten di(triphenylphosphine)iminiumchloride ((PNP)Cl) yielding cis-di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2-)zirconate(IV), cis-(PNP)[ZrCl3Pc2?]. This crystallizes with two molecules of dichloromethane in the monoclinic space group P21/n with the lattice constants a = 15.219(4) Å, b = 20.262(10) Å, c = 20.719(4) Å, b? = 93.46(2)°, Z = 4. The seven coordinated Zr atom is situated in a “square base-trigonal cap” polyhedron. The plane of the three chlorine atoms runs parallel to the plane of the four isoindole nitrogen atoms Niso. The Zr–Cl distances range from 2.49 to 2.55 Å, the Zr? Niso distances from 2.26 to 2.29 Å. Due to ion packing effects the Pc2? ligand shows an asymmetrical convex distortion. The PNP cation adopts the bent conformation. The P? N? P angle is 139°, the P? N distance 1.58 Å. As confirmed by the cyclovoltammograms cis-(PNP)[ZrCl3Pc2?] is oxidized (anodically or chemically by Cl2) to yield cis-tri(chloro)phthalocyaninato(1–)zirconium(IV) and reduced (cathodically or chemically by [BH4]?) yielding chlorophthalocyaninato(2–)zirconium(III) and cis-di(triphenylphosphine)iminium-di(chloro)phthalocyaninato(2–)zirconate(III). The optical spectra show the typical π–π*-transitions of the Pc2? resp. Pc? ligand not much affected by the different states of oxidation and coordination of zirconium. The same is true for the vibrational spectra of the Pc2? resp. Pc? ligand. In the f.i.r. spectra between 350 and 150 cm?1 the asym. and sym. Zr? Cl stretching and Cl? Zr? Cl deformation vibration as well as the asym. Zr? N stretching vibration of the [ZrClxN4] skeleton (x = 1–3) is assigned. 相似文献
15.
Synthesis and Properties of (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium, [Ru(X)(NO)pc2–] (X = F, Cl, Br, I, CN, NCO, NCS, NCSe, N3, NO2) is obtained by acidification of a solution of bis(tetra(n-butyl)ammonium) bis(nitro)phthalocyaninato(2–)ruthenate(II) in tetrahydrofurane with the corresponding conc. mineral acid or aqueous ammonium salt solution. The nitrite-nitrosyl conversion is reversal in basic media. The cyclic and differential pulse voltammograms show mainly three quasi-reversible one-electron processes at 1.05, –0.65 and –1.25 V, ascribed to the first ring oxidation and the stepwise reduction to the complexes of type {RuNO}7 and {RuNO}8, respectively. The B < Q < N regions in the electronic absorption spectra are still typical for the pc2– ligand, but are each split into two strong absorptions (14500/16500(B); 28000/30500(Q); 34500/37000 cm–1(N)), whose relative intensities strongly depend on the nature of the axial ligand X. In the IR spectra is active the N–O stretching vibration between 1827 (X = I) and 1856 cm–1 (F), the C–N stretching vibration at 2178 (X = NCO), 2072 (NCS), 2066 (NCSe), 2093 cm–1 (CN), the N–N stretching vibration of the azide ligand at 2045 cm–1, the fundamentals of the nitrito(O) ligand at 1501, 932, and 804 cm–1, and the Ru–X stretching vibration at 483 (F), 332 (Cl), 225 (Br), 183 (I), 395 (N3), 364 (ONO), 403 (CN), 263 (NCS), and 231 cm–1 (NCSe). In the resonance Raman spectra, excited in coincidence with the B region, the Ru–NO stretching vibration and the very intense Ru–N–O deformation vibration are selectively enhanced between 580 and 618 cm–1, and between 556 and 585 cm–1, respectively. 相似文献
16.
Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), cis[Tl(X)2pc2–]– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (nBu4N)X in dichloromethane, and isolated as (nBu4N)cis[Tl(X)2pc2–]. (nBu4N)cis[Tl(ONO′)2pc2–] ( 1 ) and (nBu4N)cis[Tl(X)2pc2–] · 0,5 (C2H5)2O ( 2 ) crystallize in the monoclinic space group P21/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (Niso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–Niso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four Niso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–Niso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (Niso)4 plane (CtN) towards the acido ligands (d(Tl–CtN) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed. 相似文献
17.
Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Chloro-Iodo-Rhenates(IV) (CH2Py2)[ReCl5I], cis -(CH2Py2)[ReCl4I2] · 2 DMSO, trans -(CH2Py2)[ReCl4I2] · 2 DMSO, and fac -(EtPh3P)2[ReCl3I3] [ReCl5I]2–, cis-[ReCl4I2]2–, trans-[ReCl4I2]2–, and fac-[ReCl3I3]2– have been synthesized by ligand exchange reactions of [ReI6]2– with HCl and are separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations have been performed on single crystals of (CH2Py2)[ReCl5I] ( 1 ) (triclinic, space group P1 with a = 7.685(2), b = 9.253(2), c = 12.090(4) Å, α = 90.06(2), β = 101.11(2), γ = 95.07(2)°, Z = 2), cis-(CH2Py2)[ReCl4I2] · 2 DMSO ( 2 ) (triclinic, space group P1 with a = 8.662(2), b = 12.109(2), c = 12.9510(12) Å, a = 97.533(11), β = 96.82(2), γ = 89.90(2)°, Z = 2) , trans-(CH2Py2)[ReCl4I2] · 2 DMSO ( 3 ) (triclinic, space group P1 with a = 9.315(7), b = 9.663(3), c = 15.232(3) Å, α = 80.09(2), β = 81.79(4), γ = 83.99(5)°, Z = 2) and fac-(EtPh3P)2[ReCl3I3] ( 4 ) (monoclinic, space group P21/a with a = 17.453(2), b = 13.366(1), c = 19.420(1) Å, β = 112.132(8)°, Z = 4). The crystal structure of ( 1 ) reveals a positional disorder of the anion sublattice along the asymmetric axis. Due to the stronger trans influence of I compared with Cl on asymmetric axes Cl˙–Re–I′ is caused a mean lenghthening of the Re–Cl˙ distances of 0.020 Å (0.8%) and a shortening of the Re–I′ distances of 0.035 Å (1.3%) with regard to symmetrically coordinated axes Cl–Re–Cl and I–Re–I, respectively. Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts of all four chloro-iodo-rhenates(IV) are assigned by normal coordinate analyses. The weakening of the Re–Cl˙ bonds and the strengthening of the Re–I′ bonds is indicated by a decrease or increase of the valence force constants each by 9%. 相似文献
18.
C–H-Activation: Syntheses and Properties of Acetonato( C )-acidophthalocyaninato(2–)metallates(III) of Rhodium and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Acetonato( C )azidophthalocyaninato(2–)iridate(III) Phthalocyaninato(2–)metallate(I) of rhodium and iridium reacts with carbonyl substrates like acetone or acetylacetone and halides or pseudohalides forming acetonato(C)- or acetylacetonato(C)acidophthalocyaninato(2–)metallates(III), that are isolated as tetra(n-butyl)ammonium complex salts (nBu4N)[M(R)(X)pc2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N3, SCN/NCS). (nBu4N)[Ir(aC)(N3)pc2–] · 0,25(C2H5)2O · 0,5 CH2Cl2 crystallizes in the triclinic space group P1 with cell parameters a = 16.267(8) Å, b = 17.938(3) Å, c = 18.335(4) Å, α = 74.77(2)°, β = 73.73(3)°, γ = 84.25(3)°, V = 4954(3) Å3, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a Naza bridge of the phthalocyaninate, while the σ-C bonded acetonate is always oriented towards an isoindole group (gauche and ecliptical configuration). The Ir–C distances are 2.12(1) and 2.14(1) Å. Due to the trans influence of the acetonate-C atom the Ir-azide-N distances of 2.22(1)/2.24(1) Å are longer than expected. The electrochemical properties and the optical, vibrational, and 1H-NMR spectra are discussed. 相似文献
19.
Two new hybrid fluorides, {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– ( I ) and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2 ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) Å3, Z = 1, R = 0.0489, Rw = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) Å3, Z = 1, R = 0.0327, Rw = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF6 octahedra form a [Al7F30]9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al7F29)n8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al7F309– heptamers in I and with three inorganic chains in II . 相似文献
20.
Synthesis and Properties of Diphthalocyaninates of Bismuth, [Bi(Pc)2]k (k = 1?, 0, 1+); Crystal Structure of mixed-valent [Bi(Pc)2] · CH2Cl2 Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc2?)2]?, is obtained by the reaction of BiO(NO3) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium (nBu4N)+ and bis(triphenylphosphine)iminium (PNP)+ salt. Green mixed-valent [Bi(Pc)2] · CH2Cl2 is prepared by anodic oxidation of [Bi(Pc2?)2]?. It crystallizes in the orthorhombic γ modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Å, Z = 4). The BiIII ion is eightfold coordinated by the Niso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? Niso bond distance is 2.467 Å. The complex is paramagnetic (μeff = 1.84 μB). Oxidation of [Bi(Pc2?)2]? with bromine yields purple, diamagnetic [Bi(Pc?)2]Brx (1.5 ≤ x ≤ 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides. 相似文献