Ruthenium(III)-Phthalocyanine: Darstelllung und Eigenschaften von Di(halogeno)phthalocyaninato(1−)ruthenium(III), [Ru(X)2Pc] (X = Cl,Br, I)

Ruthenium(III) Phthalocyanines: Synthesis and Properties of Di(halo)phthalocyaninato(1?)ruthenium(III) Di(halo)phthalocyaninato(1?)ruthenium(III), [Ru(X)₂Pc^?] (X = Cl, Br, I) is prepared by oxidation of [Ru(X)₂Pc^2?]^? (Cl, Br, OH) with halogene in dichloromethane. The magnetic moment of [Ru(X)₂Pc^?] is 2,48 μ_B (X = Cl) resp. 2,56 μ_B (X = Br) in accordance with a systeme of two independent spins (low spin Ru^III and Pc^?: S = 1/2). The optical spectra of the red violet solution of [Ru(X)₂Pc^?] (Cl, Br) are typical for the Pc^? ligand with the “B” at 13.5 kK, “Q₁” at 19.3 kK and “Q₂ region” at 31.9 kK. Sytematic spectral changes within the iron group are discussed. The presence of the Pc^? ligand is confirmed by the vibrational spectra, too. Characteristic are the metal dependent bands in the m.i.r. spectra at 1 352 and 1 458 cm^?1 and the strong Raman line at 1 600 cm^?1. The antisymmetric Ru? X stretch (v_as(Ru? X)) is observed at 189 cm^?1 (X = I) resp. 234 cm^?1 (X = Br). There are two interdependent bands at 295 and 327 cm^?1 in the region expected for v_as(Ru? Cl) attributed to strong interaction of v_as(Ru? Cl) with an out-of-plane Pc^? tilting mode of the same irreducible representation. Only the symmetric Ru? Br stretch at 183 cm^?1 is selectively enhanced in the resonance-Raman(RR) spectra. The Raman line at 168 cm^?1 of the diiodo complex is assigned to loosely bound iodine. The broad band at 978 cm^?1 in the RR spectra of the dichloro complex is due to an intraconfigurational transition within the electronic ground state of low spin Ru^III split by spin orbit coupling.     

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.     

Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

CrIII-Phthalocyaninate: Darstellung,Eigenschaften und Kristallstruktur von l-Bis(triphenylphosphin)iminium-trans-di(nitrito(O))phthalocyaninato(2–)-chromat(III)

Cr^III Phthalocyaninates: Synthesis, Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Di(nitrito(O))phthalocyaninato(2–)chromate(III) [Cr(H₂O)₂Pc^2?]I_x 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)₂Pc^2?], which crystallizes in the triclinic space group P1 (No. 2) with Z = 2. The Cr atom is in the center of the Pc^2? ligand and the two nitrite ions are monodentate O-coordinated in a mutually trans arrangement to the Cr atom. The Cr? O and Cr? N_iso 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 Pc^2? 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 Pc^2? 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, v_s(Cr? O) at 378 cm^?1 is selectively resonance Raman (RR) enhanced. v_as(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: v_as(N? O)/1447 > v_as(N? O)/1018/1029 > δ(O? N? O)/828 and in the RR-spectrum: v_s(N? O)/1410 > v_s(N? O)/952, the last followed by three overtones.     

Darstellung und Eigenschaften von (Acido)(pyridin)phthalocyaninato(2–)ruthenaten(II); Kristallstruktur von Tetra(n-butyl)ammonium(cyano)(pyridin)phthalocyaninato(2–)ruthenat(II)

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)pc^2–] (X = CN, N₃, NCS, NCO, NO₂). (ⁿBu₄N)[Ru(CN)(py)pc^2–] 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 (N_iso)₄ plane (N_iso: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (N_iso)₄ plane towards cyanide (d(Ru–Ct)) is 0.020 Å. The Ru–N_iso distance varies from 1.947(2) to 1.992(2) Å. The average Ru–C and Ru–N_py distance is 2.00 Å and 2.19 Å, respectively. The pc^2– ligand ist slightly distorted towards the cyanide. The cyclic and differential pulse voltammograms of (ⁿBu₄N)[Ru(X)(py)pc^2–] 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)pc^2–] are discussed.     

Darstellung und spektroskopische Charakterisierung von Di(halogeno)phthalocyaninato(1–)rhodium(III), [RhX2Pc1−] (X = Cl,Br, I)

Synthesis and Spectroscopical Characterization of Di(halo)phthalocyaninato(1–)rhodium(III), [RhX₂Pc^1?] (X = Cl, Br, I) Bronze-coloured di(halo)phthalocyaninato(1–)-rhodium(III), [RhX₂Pc^1?] (X = Cl, Br) and [RhI₂Pc^1?] · I₂ is prepared by oxidation of (ⁿBu₄N)[RhX₂Pc^2?] with the corresponding halogene. Irrespective of the halo ligands, two irreversible electrode reactions due to the first ringreduction (E_R = ?0,90 V) and ringoxidation (E_O = 0,82 V) are present in the cyclovoltammogram of (ⁿBu₄N)[RhX₂Pc^2?]. The optical spectra show typical absorptions of the Pc^1?-ligand at 14.0 kK and 19.1 kK. Characteristic vibrational bands are at 1 366/1 449 cm^?1 (i. r.) and 569/1 132/1 180/1 600 cm^?1 (resonance Raman (r. r.)). The antisym. (Rh? X)-stretching vibration is observed at 294 cm^?1 (X = Cl), 240 cm^?4 (Br) and 200 cm^?1 (I). Only the sym. (Rh? I)-stretching vibration at 133 cm^?1 is r. r. enhanced together with a strong line at 170 cm^?1, which is assigned to the (I? I)-stretching vibration of the incorporated iodine molecule. Both modes show overtones and combinationbands.     

InIII-Phthalocyanine: Darstellung,Eigenschaften und Kristallstruktur von Tetra(n-butyl)ammonium-cis-di(nitrito-O,O′)phthalocyaninato(2–)indat(III)

In^III-Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)ammonium-cis-di(nitrito-O,O')phthalocyaninato(2–)indate(III) [In(Cl)Pc^2?] reacts with (ⁿBu₄N)NO₂ in acetone yielding green-blue (ⁿBu₄N)^cis[In(NO₂)₂Pc^2?], which crystallizes in the monoclinic space group P2₁/n (No. 14). Both nitrite anions are coordinated as chelating nitrito-O,O'(NO₂) ligands to In^III in cis-geometry. Consequently In^III is octa-coordinated within a distorted “quadratic” antiprism and directed towards the Pc^2?-ligand. One of the NO₂ ligands has equivalent N? O bonds similar to free nitrite, while the other has asymmetric N? O bonds. Both (In,O,N,O) rings are approximately planar with a dihedral angle of 80°. The Pc^2? ligand is distorted in an asymmetrically convex manner. Partially overlapping pairs of Pc^2? ligands related by an inversion center form double layers, which are separated by layers containing the (ⁿBu₄N)⁺ cations. The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc^3?/Pc^2? (?0.94 V) < In^I/In^III (-0.78 V) < Pc^2?/Pc^? (0.64 V). The UV-VIS-NIR spectra and vibrational spectra are discussed.     

Darstellung und spektroskopische Eigenschaften von Di(phthalocyaninato(1−))-lanthanidpolybromid; Kristallstruktur von α-Di(phthalocyaninato)samariumpolybromid, α-[Sm(Pc)2]Br1,45 und α-Di(phthalocyaninato)samariumperchlorat, α-[Sm(Pc)2](ClO4)0,63

Synthesis and Spectroscopical Properties of Di(phthalocyaninato(1?))lanthanidepolybromide; Crystal Structure of α-Di(phthalocyaninato)samariumpolybromide, α-[Sm(Pc)₂]Br_1.45 and α-Di(phthalocyaninato)samariumperchlorate, α-[Sm(Pc)₂](ClO₄)_0.63 Bronze-coloured di(phthalocyaninato)lanthanidepolybromide, [Ln(Pc^?)₂]Br_y (Ln = La…(? Ce, Pm)…Lu; y > 1.5) is prepared by oxidation of (ⁿBu₄N)[Ln(Pc^2?)₂] with bromine in excess. The UV-VIS-NIR spectra show the typical B and Q₁ bands of the Pc^? ligand at ～ 14 kK and ～ 20 kK. For the [Ln(Pc^?)₂]⁺ cation a NIR(D) band between 9,14 kK (La) and 11,50 kK (Lu) is characteristic for dimeric cofacial Pc^? radicals. Within the row La…Lu, there is a linear relationship of the hypsochromic shift of the strong bands and the Ln^III radius. In the case of La? Nd the D band shifts successively with longer time of bromination to ～ 3 kK as a result of increasing electron delocalisation. Characteristic vibrational bands are at ～ 1350/1450 cm^?1 (IR) and ～ 560/1120/1170/1600 cm^?1 (RR). In the FT-Raman spectra the totally symmetric Ln? N stretching vibration between 141 cm^?1 (La) and 172 cm^?1 (Lu) is selectively enhanced. As shown by α-[Sm(Pc)₂]Br_1,45 and α-[Sm(Pc)₂](ClO₄)_0,63 only partially ringoxidized complexes are obtained by the anodic oxidation. Both crystallize in the tetragonal space group P4/nnc. The [Sm(Pc)₂] molecular building block contains two nearly planar staggered (～41°) Pc rings packed in columns parallel along [001] leading to the quasi-one-dimensional structure. There is a statistical disorder of the Sm^III and the ClO₄^? resp. Br^?/Br₃^? ions over two incompletely filled crystallographic positions for the cation resp. anion. This results in a partial oxidation of the Pc ligand, which in the picture of localized valence states for α-[Sm(Pc)₂](ClO₄)_0,63 corresponds to [SmPc^?Pc^2?] · 2[Sm(Pc^?)₂](ClO₄). Accepting the same valence state for [Sm(Pc)₂]Br_1,45 five positive charges are compensated by two Br^? and three Br₃^?. The spectroscopic differences of the partially and fully oxidized complexes are discussed.     

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.     

Darstellung und Eigenschaften von Phthalocyaninato(2–)indaten(III) mit einzähnigen Acido-Liganden; Kristallstruktur von Tetra(n-butyl)ammonium-cis-difluoro-Phthalocyaninato(2–)indat(III)-Hydrat

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)₂pc^2–] · 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 (N_iso) and two cis-positioned fluorine atoms. The average In–F and In–N_iso 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 N_iso plane towards the fluoride ligands: d(In–Ct) = 0.953(1) Å. The phthalocyaninato(2–) core is nonplanar (unsymmetrical concave distortion).     

C–H-Aktivierung: Synthese und Eigenschaften von Acetonato(C)acidophthalocyaninato(2–)metallaten(III) von Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumacetonato(C)-azidophthalocyaninato(2–)iridat(III)

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)pc^2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N₃, SCN/NCS). (ⁿBu₄N)[Ir(aC)(N₃)pc^2–] · 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) ų, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a N_aza 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.     

Darstellung und Eigenschaften von tetragonalen α-Di(phthalocyaninato(1−))-praseodym(III)-polyhalogeniden; Kristallstruktur von α-[Pr(Pc−)2]Br1,5

Preparation and Properties of Tetragonal α-Di(phthalocyaninato(1?))praseodymium(III)-polyhalides; Crystal Structure of α-[Pr(Pc^?)₂]Br_1.5 Brown red di(phthalocyaninato(1?))-praseodym(III)-polyhalides [Pr(Pc^?)₂]X_y (X = Br, I) of variable composition (1 ≤ y ≤ 2.5) are formed by (electro)chemical oxidation of [Pr(Pc^2?)₂]^?. The thermical decomposition of these polyhalides at 250°C yields partially oxidized, green α-[PrPc^?Pc^2?]. Due to strong spin–spin coupling of the phthalocyanin-π-radicals only Pr^III contributes to the magnetic moment of ca. 3.0 B.M. for all complexes. Green metallic prisms of [Pr(Pc^?)₂]Br_1.5 crystallize in the tetragonal α-modification: space group P4/nnc with a = 19.634(5) Å, c = 6.485(2) Å; Z = 2. In the sandwich complex Pr^III is eightfold coordinated by the isoindoline N-atoms of the two staggered (41°), nearly planar Pc^?- ligands. The quasi-onedimensional character of the structure along [001] is due to the infinite columns of Pc^? ligands. The superperiod along [001] is a consequence of the distribution of the Pr atoms onto two incompletely filled crystallographic positions at a distance of c/2 and the disordered chains of the bromine atoms extending in the same direction. Powder diffractograms of Pr(Pc )₂Br2, [Pr(Pc^?)₂]I₂ und [PrPc Pc^2?] confirm the tetragonal α-modification of these complexes, too. The content of tribromide correlates with the population of the Pr(2)-site. In the UV-VIS-NTR absorption spectrum of a thin film of Pr(Pc )₂Br, the intense bands at 13.9 and 19.5 kK are assigned to the B and Q transition, respectively. The D band at 9. kK is characteristic for isolated dimeric Pc^?-π-radicals. Due to increasing electron delocalisation as a result of the growing columns the D band is shifted to lower energy appearing successively at 6.05 and 3.3 kK. The mir and resonance Raman (RR) spectra of α-[Pr(Pr^?)₂]X_y, (X = Br, I) show the well known diagnostic bands for Pc^?-π-radicals. Thc RR spectrum of the polyiodide is dominated by the overtone progression of the totally symmetric (I-I) stretching vibration of the triiodide at 108cm^?1. The FT-Raman spectra are also marked by the totally symmetric stretching vibration of the polyhalides (Br₃ : 145cm ¹; 1₃^?:105cm^?1; I₅^? 151 cm^?1).     

Darstellung und Eigenschaften der Phthalocyaninato(2–)metallate(I) von Cobalt,Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumphthalocyaninato(2–)cobaltat(I)-Aceton-Solvat

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–N_iso 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 pc^2– 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 → pc^2– charge transfer transitions. The vibrational spectra are typical for the pc^2– ligand. The very low absorbance of the IR bands at 916/1067/1330 cm^–1 is diagnostic for low-valent metal phthalocyaninates.     

Zirconiumphthalocyanine: Darstellung und Eigenschaften chloridhaltiger Phthalocyanine des drei- und vierwertigen Zirconiums; Kristallstruktur von cis-Di(triphenylphosphin)iminium-tri(chloro)phthalocyaninato(2–)zirconat(IV)-di(dichlormethan)

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)[ZrCl₃Pc^2?]. 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 N_iso. The Zr–Cl distances range from 2.49 to 2.55 Å, the Zr? N_iso distances from 2.26 to 2.29 Å. Due to ion packing effects the Pc^2? 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)[ZrCl₃Pc^2?] 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 Pc^2? 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 Pc^2? 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 [ZrCl_xN₄] skeleton (x = 1–3) is assigned.     

Synthese und Eigenschaften von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(halogenophthalocyaninato(2–)ferraten(IV)); Kristallstruktur von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(fluorophthalocyaninato(2–)ferrat(IV))-Trihydrat

Synthesis and Properties of Bis(tetra(n-butyl)ammonium)μ-Carbido-di(halophthalocyaninato(2–)ferrates(IV)); Crystal Structure of Bis(tetra(n-butyl)ammonium) μ-Carbido-di(fluorophthalocyaninato(2–)ferrate(IV)) Trihydrate μ-Carbido-di(pyridinephthalocyaninato(2–)iron(IV)) reacts with tetra(n-butyl)ammonium halide (ⁿBu₄N)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium μ-carbido-di(halophthalo-cyaninato(2–)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12₁/n1 with the following cell parameters: a = 15.814(1) Å; b = 22.690(5) Å; c = 25.127(3) Å; β = 98.27(1)°, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N_iso)₄ planes (N_iso: isoindoline-N atom) with a Fe–Ct distance of 0.053(1) Å. The average Fe–N_iso distance is 1.939(4) Å, the Fe–(μ-C) distance 1.687(4) Å and the Fe–F distance 2.033(2) Å. The Fe–(μ-C)–Fe core is linear (179.5(3)°). The pc²-ligands are staggered (φ = 42(1)°) with a convex distortion. The asymmetric Fe–(μ-C)–Fe stretch (in cm^–1) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe–(μ-C)–Fe stretch at 476 cm^–1 in the resonance Raman spectra. The IR active asymmetric Fe–X stretch (in cm^–1) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively.     

Darstellung und Kristallstruktur von Kupfer(II)-monofluorophosphat-Dihydrat CuPO3F · 2H2O

Salts of Halogenophosphoric Acids. XVII. Preparation and Crystal Structure of Copper(II) Monofluorophosphate Dihydrate CuPO₃F · 2H₂O Copper(II) monofluorophosphate dihydrate, CuPO₃F · 2H₂O 1 was obtained by the reaction of aqueous NH₄HPO₃F and acid (NH₄)₂PO₃F solutions, respectively, using acetone or ethanol as precipitating agents. The thermal dehydration of 1 gives the water-free copper monofluorophosphate CuPO₃F ( 2 ). 1 crystallizes in the monoclinic space group P2₁/c with a = 761,44, b = 780,97, c = 921,02 pm, β = 112,94° and Z = 4.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

CrIII-Phthalocyaninate: Darstellung und spektroskopische Eigenschaften von Di(halogeno)phthalocyaninatochromaten(III)

Cr^III Phthalocyaninates: Synthesis and Spectroscopical Properties of Di(halo)phthalocyaninato(2 –)chromates(III) [Cr(H₂O)₂Pc^2?]⁺ reacts in acetone with (ⁿBu₄N)X to yield less soluble tetra(n-butyl)ammonium di(halo)phthalocyaninato(2 –)chromate(III), (ⁿBu₄N)[Cr(X)₂Pc^2?] (X = F, Cl, Br, I). In the differential pulse voltammograms the first ring oxidation is observed at 0,80 V, the ring reduction at ?1,48 V and the metal reduction (Cr(III)/Cr(II)) at ?0,80 V (averaged potentials). The last is followed by a partial dissociation of one of the halo ligands. In the UV-VIS-NIR spectra there are three weakly absorbing spin-allowed trip-quarter(TQ) transitions (TQ1 (8,4) < TQ2 (11,5) < TQ3 (20,6); averaged values (av) in 10³ cm^?1), a (Pc + X)-CrCT transition (31,3; av in 10³ cm^?1) and the characteristic π-π* transitions of the Pc^2? ligand (B (14,5) < Q₁ (24,5) < Q₂ (29,2) < N (36,0) < L (41,0); av in 10³ cm^?1). Q₁ and (Pc + X)-CrCT depend strongly on the halo ligands. Prominent luminescence spectra are obtained by excitation within the TQ1 region, in which the spin-forbidden trip-sextet transition (8330 (X = F), 7680 (Cl), 7460 (Br) 7450 cm^?1 (I)) dominates at low temperatures (T < 50 K). The vibrational spectra are discussed. In coincidence of the excitation lines with TQ3, v_s(Cr? X) at 458 (X = F) < 246 (Cl) < 157 (Br) < 107 cm^?1 ( I ) is selectively resonance Raman enhanced. v_as(Cr? X) is observed in the FIR spectrum at 522 (X = F) < 283/326 (Cl) < 227 (Br) < 205 cm^?1 ( I ).     

Darstellung und Eigenschaften von trans-Di(fluoro)phthalocyaninato(2–)-rhenat(III); Kristallstruktur des linear-Bis(triphenylphosphin)iminium-Doppelsalzes l(PNP)trans[Re(F)2pc2–] · 0,33l(PNP)F · 2 H2O

Synthesis and Properties of trans -Di(fluoro)phthalocyaninatorhenate(III); Crystal Structure of the linear -Bis(triphenylphosphine)iminium Double Salt ^l (PNP) ^trans[Re(F)₂pc^2–] · 0.33^l (PNP)F · 2 H₂O trans-Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II) reacts with (ⁿBu₄N)F · 3 H₂O in acetone on air yielding trans-di(fluoro)phthalocyaninato(2–)rhenate(III), ^trans[Re(F)₂pc^2–]^–. The complex anion is precipitated as tetra(n-butyl)ammonium (ⁿBu₄N), or after addition of (PNP)HSO₄ as linear-bis(triphenylphosphine)iminium (^l(PNP)) salt. The latter crystallizes as a double salt of formula ^l(PNP)^trans[Re(F)₂pc^2–] · 0.33^l(PNP)F · 2 H₂O in the cubic space group I23 (no. 197) with the cell parameter a = 21.836(2) Å; V = 10412(2) ų; Z = 6. The Re atom is located in the centre of the (N_iso)₄ plane (N_iso: isoindole-N atom) and coordinates axially two fluorine atoms in a mutual trans position. The Re–N and Re–F distance is 2.035(6) and 1.798(7) Å, respectively. According to the short Re–F distance the asymmetric Re–F stretching vibration is observed in the MIR spectrum at 746 cm^–1. Obviously due to a large spin-orbit coupling, the complex salt with an electronic low-spin d⁴ ground state of Re^III (S = 1) is diamagnetic. Hence a sharp signal is observed at –126.1 ppm in the ¹⁹F NMR spectrum. The UV-VIS-NIR spectrum shows the typical π-π* transitions at 15000 (B), 29500 (Q) and 36900 cm^–1 (N) and trip-multiplet transitions at 9500/10500 cm^–1 and 13200/14100 cm^–1.     

Darstellung und Kristallstruktur von Cobalt(II)-Hexaoxodiphosphat(P?P)(4−)-dodecahydrat,Co2P2O6 · 12 H2O

Synthesis and Crystal Structure of Cobalt(II)-hexaoxodiphosphate(P? P)(4?)-dodecahydrate, Co₂P₂O₆ · 12 H₂O Co₂P₂O₆ · 12H₂O was obtained by cleavage and simultaneous oxidation of cyclo-hexaphosphate(III) in a solution of ethanol and aqueous ammonia. The crystal structure has been determined (1 898 independent diffractometer data): space group Pbam (No. 55), a = 6.710(2), b = 12.196(2), c = 10.073(3) Å, V = 825.3(1) ų, Z = 2, R = 0.060. The P₂O₆^4? anions show site symmetry C_2h and are connected to form chains via cobalt. Two cobalt ions together with two sets of four water molecules and two oxygen atoms of P₂O₆^4? form pairs of edge connected octahedra. The common edges are formed by the oxygen atoms of the P₂O₆ groups.