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.     

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.     

OsII-Phthalocyaninate(2−): Darstellung und Eigenschaften von (Halogeno)-(carbonyl)phthalocyaninato(2−)osmat(II)

Os^II Phthalocyaninates(2?): Synthesis and Properties of (Halo)(carbonyl)phthalocyaninato-(2?)osmate(II) Soluble, blue tetra(n-butyl)ammonium (halo)(carbonyl)phthalocyaninato(2?)osmate(II), (ⁿBu₄N)[Os(X)(CO)Pc^2?] (X = Cl, Br, I) is obtained by the reaction of [Os(THF)(CO)Pc^2?] (THF: tetrahydrofurane) with (ⁿBu₄N)X in THF. In the cyclovoltammograms there are three reversible electrode processes at ?1.21 ± 0.01, 0.18 ± 0.04 and 0.65 ± 0.01 V assigned to the three redox pairs Pc^2?/Pc^3?, Os^II/Os^III and Pc^2?/Pc^3?. In the electronic absorption spectra only the intense B and Q regions are observed at ～ 15800 resp. 27500, 33000 cm^?1. The infrared and resonance Raman spectra closely resemble those of other phthalocyaninates(2?) of low valent osmium. In the infrared spectrum v(C? O) is detected at 1896 ± 4 cm^?1 and v(Os? X) at 260 (X = Cl), 175 (X = Br) or 143 cm^?1 (X = I).     

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.     

Ruthenium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(halogeno)phthalocyaninatoruthenat(II)

Ruthenium(II) Phthalocyanines: Preparation and Properties of Di(halo)phthalocyaninatoruthenate(II) [Ru(Py)₂Pc^2?] reacts with molten (ⁿBu₄N)X forming stable, green (ⁿBu₄N)₂[Ru(X)₂Pc^2?] (X = Cl, Br). The cyclovoltammogram shows a quasireversible redoxprocess for the metal oxidation at E_1/2(I) = ?0.02 V (X = Cl) resp. 0.05 V (X = Br) and for the first ringoxidation at E_1/2(II) = 0.70 V. The typical π-π*-transitions (B < Q < N) of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. With respect to Ru^III phthalocyanines B is shifted significantly to higher, Q, N to lower energy. The strong extra-band at 24.2 kK is diagnostic for these Ru^II phthalocyanines. The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry, too, and bands at 513, 909, 1 171 und 1 329 cm^?1 in the m.i.r. spectrum are specific for hexa-coordinated low spin Ru^II. In the Raman spectrum with excitation at ～480 nm the intensity of the totally symmetrical Ru? X stretching vibration at 266 cm^?1 (X = Cl) resp. 168 cm^?1 (X = Br) together with a progression of up to three overtones is selectively resonance Raman enhanced. The asymmetrical Ru? X stretching vibration is observed in the f.i.r. spectrum at 272 cm^?1 (X = Cl) resp. 215 cm^?1 (X = Br).     

Osmium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(acido)phthalocyaninatoosmaten(II)

Osmium(II) Phthalocyanines: Preparation and Properties of Di(acido)phthalocyaninatoosmates(II) “H[Os(X)₂Pc^2?]” (X = Br, Cl) reacts in basic medium or in the melt with (ⁿBu₄N)X forming less stable, diamagnetic, darkgreen (ⁿBu₄N)₂[Os(X)₂Pc^2?]. Similar dicyano and diimidazolido(Im) complexes are formed by the reaction of “H[Os(Cl)₂Pc^2?]” with excess ligand in the presence of [BH₄]^?. The cyclic voltammograms show up to three quasireversible redoxprocesses: E_1/2(I) = 0.13 V (X = CN), ?0.03 V (Im), ?0.13 V (Br) resp. ?0.18 V (Cl) is metal directed (Os^II/III), E_1/2(II) = 0.69 V (Cl), 0.71 V (Br), 0.83 V (CN), 1.02 V (Im) is ligand directed (Pc^2?/?) and E_1/2(III) = 1.17 V (Cl) resp. 1.23 V (Br) is again metal directed (Os^III/IV). Between the typical “B” (～16.2 kK) and “Q” (～29.4 kK), “N regions” (～34.1 kK) up to seven strong “extra bands” of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. Within the row CN > Im > Br > Cl, most of the bands are shifted slightly, the “extra bands” considerably more to lower energy in correlation with E_1/2(I). The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry. M.i.r. bands at 514, 909, 1 173 and 1 331 cm^?1 are specific for hexa-coordinated low spin Os^II phthalocyanines. In the resonance Raman (r.r.) spectra polarized, depolarized or anomalously polarized deformation and stretching vibrations of the Pc^2? ligand will be selectively enhanced, if the excitation frequency coincides with “extra bands”. With excitation at ～19.5 kK the intensity of the symmetrical Os? X stretching vibration at 295 cm^?1 (X = Cl), 252 cm^?1 (X = Im) and 181 cm^?1 (X = Br) is r.r. enhanced, too. The asymmetrical Os? X stretching vibration is observed in the f.i.r. spectrum at 345 cm^?1 (X = CN), 274 cm^?1 (X = Cl), 261 cm^?1 (X = Im) and 200 cm^?1 (X = Br).     

Synthese und Eigenschaften von (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium

Synthesis and Properties of (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium, [Ru(X)(NO)pc^2–] (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 pc^2– 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.     

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).     

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 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.     

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.     

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.     

High-spin Mangan(II)-Phthalocyanine: Darstellung und spektroskopische Eigenschaften von Acidophthalocyaninatomanganat(II)

High Spin Manganese(II) Phthalocyanines: Preparation and Spectroscopical Properties of Acidophthalocyaninatomanganate(II) Acidophthalocyaninatomanaganese(III) is reduced by boranate, thioacetate or hydrogensulfide to yield acidophthalo-cyaninatomanganate(II) ([Mn(X)Pc^2?]^?; X = Cl, Br, NCO, NCS) being isolated as tetra(n-butyl)ammonium salt. In the cyclovoltammogram of [Mn(NCO)Pc^2?]^? the halv-wave potential for the redoxcouple Mn^II/Mn^III is at ?0.13 V, that of the first ring reduction at ?0.99 V. The magnetic moments are indicative of high-spin ⁶A₁ ground states: μ_Mn = 5.84 (NCO), 5.78(Cl), 5.65 (Br), 5.68 μ_B (NCS). A Curie-like temperature dependence of μ_Mn is observed in the region 300–30 K. Below 30 K an increase in μ_Mn occurs due to weak intermolecular ferromagnetic coupling. The ESR spectra confirm the S = 5/2 ground state with a strong g = 6 resonance observed (A_Mn = 80 G) as expected for an axially distorted ligand-field. Besides the typical π-π* transitions of the Pc^2?-ligand several weak bands are observed in the Uv-vis-n.i.r. spectra at ca. 7.5, 9.1, 14.0 and 19.0 kK that are assigned to trip-multiplet transitions. In resonance with the band at 19.0 kK the Mn? X stretching vibration (v(MnX)) is resonance Raman enhanced: X = NCO: 319, Cl: 286, SCN: 238, Br: 202 cm^?1. These vibrational frequencies are confirmed by the f.i.r. spectra. In the case of the thiocyanato-complex probably both forms of bonding of the ambident NCS-ligand are present (v(Mn? NCS): 274 cm^?1). The frequencies of the vibrations of the inner (CN)₈ ring are reduced by up to 20 cm^?1 as compared with those of low spin Mn^II phthalocyanines.     

Darstellung und spektroskopische Eigenschaften der gemischtvalenten Di(phthalocyaninato)lanthanide(III)

Synthesis and Spectroscopical Properties of the Mixed-Valent Di(phthalocyaninato)lanthanides(III) Green di(phthalocyaninato)lanthanide(III), [M(Pc)₂] (M = rare earth metal ion: La‥(-Ce, Pm)‥Lu) is prepared by anodic oxidation of (ⁿBu₄N)[M(Pc^2?)₂] dissolved in CH₂Cl₂/(ⁿBu₄N)ClO₄. The UV-Vis-NIR spectra show intense π-π* transitions at ? 15000 cm^?1 and 31000 cm^?1, typical for Pc^2? ligands. Bands at ? 11000 cm^?1 and 22000 cm^?1 indicate the equal presence of a Pc^? π-radical. The metal dependent NIR band between 4000 and 9000 cm^?1 is characteristic for these mixed-valent complexes and assigned to an intervalence transition (b₁ → a₂; D_4d symmetry). Most bands are shifted linearly with the M^III radius. In the IR and resonance Raman (r.r.) spectra the typical vibrations of the Pc^? π-radical are dominant. These are essentially metal independent excepting the C? C and C? N vibrations of the inner (CN)₈ ring. The sym. M? N stretching vibration between 141 (La) and 168 cm^?1 (Lu) is selectively r.r.-enhanced when excited with 1064 nm.     

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.     

Spektroskopische Eigenschaften von HCl-Addukten der Di(phthalocyaninato(2–))lanthanidsäuren

Spectroscopic Properties of HCl Adducts of the Di(phthalocyaninato(2–))lanthanide Acids Thin films of bis(triphenylphosphine)iminiumdi(phthalocyaninato(2–))lanthanidates(III), (PNP)[Ln(Pc²)₂] (Ln = La…(? Ce, Pm)…Lu) react with hydrogen chloride yielding the green acid adduct [HLn(Pc^2?)₂] · xHCl. The typical π–π* transitions of the Pc^2? ligand are observed in the UV-VIS spectra (B: ～ 14500 cm^?1; Q: ～ 30300 cm^?1); these are broadened and shifted to lower energy with respect to those of the precursor. A N? H stretching vibration at ～ 3170 cm^?1 as well as a H? N? C deformation vibration at ～ 1200 cm^?1 in the MIR spectra are diagnostic for these HCl adducts.     

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 Diphthalocyaninaten des Bismuts, [Bi(Pc)2]k (k = 1−, 0, 1+); Kristallstruktur von gemischtvalentem [Bi(Pc)2] · CH2Cl2

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(Pc^2?)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(Pc^2?)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 Bi^III ion is eightfold coordinated by the N_iso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? N_iso bond distance is 2.467 Å. The complex is paramagnetic (μ_eff = 1.84 μ_B). Oxidation of [Bi(Pc^2?)₂]^? with bromine yields purple, diamagnetic [Bi(Pc^?)₂]Br_x (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.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species

The reactions of [Ru(H)(Cl)(CO)(PPh₃)₃] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [Ru^II(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru^II(tcsq)(Cl)(CO)(PPh₃)₂], respectively. The reaction of [Ru(H)₂(CO)(PPh₃)₃] with tcq has furnished [Ru^II(tcsq)(H)(CO)(PPh₃)₂]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh₃)₂] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μ_B) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-³¹P atoms (A_iso17 G). The stretching frequency of the CO ligand increases by 20 cm⁻¹ in going from [Ru(dbsq)(Cl)(CO)(PPh₃)₂] to [Ru(tcsq)(Cl)(CO)(PPh₃)₂] consistent with electron withdrawal by chloro substituents. For the same reason the E_1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru(tcsq)(Cl)(CO)(PPh₃)₂].