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.     

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.     

Monomere und dimere Chrom(III)-Phthalocyanine: Synthese und Eigenschaften von Hydroxopyridinophthalocyaninatochrom(III) und μ-Oxodi(pyridinophthalocyaninatochrom(III))

Monomeric and Dimeric Chromium(III) Phthalocyanines: Synthesis and Properties of Hydroxopyridinophthalocyaninatochromium(III) and μ-Oxodi(pyridinophthalocyaninatochromium(III)) Heating of ?[Cr(OH)Pc^2?]”? in pyridine (Py) gives the paramagnetic (T = 273 K) complexes [Cr(OH)(Py)Pc^2?] (μ_Cr = 3.84 μ_B) and [(Cr(Py)Pc^2?)₂O] (μ_Cr = 1.24 μ_B) by consecutive substitution and condensation reactions. The UV-VIS spectra are characterized by the typical B, Q, and N regions of the Pc^2? ligand being shifted hypsochromically for the dimer with respect to the monomer due to excitonic coupling (1.5 kK). Regions of weak absorbance between 8 and 13 resp. 19 kK are assigned to trip-quartet transitions for both complexes. A weak band at 870 cm^?1 in the FIR/MIR spectra is assigned to v_as(Cr? O? Cr). In the resonance Raman(RR) spectra v(Cr? O) at 514 cm^?1 resp. v_s(Cr? O? Cr) at 426 cm^?1 is selectively enhanced. Further strong RR-lines of the μ-Oxo dimer at 110 and 631 cm^?1 are assigned to a (Py? Cr? O)- resp. internal pyridine deformation of a_1g symmetry. An assignment as 2v_as(Cr? O? Cr) is proposed for the remarkable RR line at 1740 cm^?1.     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

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.     

NiH3IO6 · 6H2O — Kristallstruktur und Schwingungsspektren

NiH₃IO₆ · 6 H₂O — Crystal Structures and Vibrational Spectra The crystal structure of NiH₃IO₆ · 6 H₂O has been determined by X-ray single-crystal diffraction (Pc, Z = 2, a = 516.74(9), b = 981.5(2), c = 1052.5(2) pm, β = 116.496(8)°) on the basis of 4169 unique reflections (R = 1.96%). The structure is built up of distorted Ni(H₂O)₆²⁺ and H₃IO₆^2? octahedra linked by hydrogen bonding. IR and Raman spectra of both the title compound and isostructural MgH₃IO₆ · 6 H₂O as well as of deuterated specimens are given. There are up to 14 different OH(OD) modes in the spectra of isotopically dilute samples due to the 15 different hydrogen positions of the structure. The internal modes of the meridional H₃IO₆^2? ions (pseudo C_2v symmetry) are discussed with respect to that double T-shaped entity, which gives rise to only two instead of 3I? O, I? O(H), and OH stretches in the IR and Raman spectra, i.e. the same as for facial (C_3v) structured ions.     

Gitterschwingungsspektren. LXIII. Be(lO3)2 · 4 H2O,ein Hydrat mit ungewöhnlicher Bindungsstruktur und Gitterdynamik

Lattice Vibration Spectra. LXIII. Be(IO₃)₂ · 4 H₂O, a Hydrate with Unusual Bonding and Lattice Dynamics The IR and Raman spectra (4000–50 cm^?1) of Be(IO₃)₂ · 4 H₂O and of deuterated specimens are recorded at 90 and 300 K and discussed in terms of the unusual relations of the masses of the atoms involved and the large polarization power of the beryllium ions. Thus, the translatory modes of the Be²⁺ ions (BeO₄ skeleton vibrations), the librations of the H₂O molecules, and the internal vibrations of the IO₃^? ions in the spectral regions of 300–400 and 600–1000 cm^?1 couple and coincide producing unusual v_H/v_D isotopic ratios of partly < 1. The H-bond donor strengths of the water molecules is so much increased (due to the very large ionic potential of Be²⁺ ions, viz. 49 e nm^?1) (synergetic effect) that the H-bonds formed are similar in strength as those in hydrates of hydroxides with the very strong H-bond acceptor group OH^? (v_OD of matrix isolated HDO molecules 2 074 and 2 244 (H₂O I) and 2 206 and 2 349 cm^?1 (H₂O II))     

Molekulares S=GeCl2 Matrix-IR-Untersuchungen und ab initio SCF-Rechnungen

The Molecule S?GeCl₂. Matrix IR Investigation and Ab initio SCF Calculation Molecular S?GeCl₂ is found in a matrix reaction between the high-temperature molecule Ge?S and Cl₂. A structure analog to that of phosgene can be derived from the isotopical shifts (⁷⁰Ge/⁷²Ge/⁷³Ge/⁷⁴Ge/⁷⁶Ge and ³⁵Cl/³⁷Cl) within the IR spectra. The normal coordinate analysis results for the Ge?S force constant a value of 4.21 mdyn/Å. The spectroscopic results are confirmed by ab initio SCF calculations.     

Gitterschwingungsspektren. LXXVI. Zur Kenntnis basischer Kupfersalze — Kristallstruktur und schwingungsspektroskopische Untersuchungen an Cu2(OH)3NO2

Lattice Vibration Spectra. LXXVI. On Basic Copper Salts — Crystal Structure, IR and Raman Spectra of Cu₂(OH)₃NO₂ Single-crystal X-ray as well as IR and Raman data of Cu₂(OH)₃NO₂ are presented and discussed with respect to an order-disorder (OD) phase transition and the strength of hydrogen bonds. Cu₂(OH)₃NO₂ crystallizes pseudosymmetrically in the monoclinic space group P2₁/m (Z = 2, a = 562.22(4), b = 605.94(5), c = 663.55(4) pm and β = 95.415(5)°) forming a layered structure of edge-connected, elongated CuO₆ octahedra (final R value 2.5% for 1047 symmetry averaged reflections with I ≥ 2.5 μ₁). The NO₂^? ions are on a split position with dynamic disordering at ambient temperature. On temperature lowering the disorder is frozen out with a symmetry decrease to space group P2₁. The disorder of the NO₂^? ions causes four different arrangements of OH₍₂₎^? with different strengths of the H…O hydrogen bonds present OD stretching modes in the spectra of isotopically dilute samples 2628, 2535, 2435, and 2343 cm^?1 at 90 K. The OH₍₁₎^? ions form weak H…N H-bonds to the lone-pair of the nitrogen atoms of the NO₂^? ions (v_OD 2563 cm^?1).     

Dimere low-spin Eisen(III)-Phthalocyanine: Synthese und Eigenschaften ferromagnetisch gekoppelter μ-Oxodi(acidophthalocyaninatoferrate(III))

Dimeric Low-Spin Iron(III) Phthalocyanines: Synthesis and Properties of Ferromagnetically Coupled μ-Oxodi(acidophthalocyaninatoferrates(III)) μ-Oxodi(phthalocyaninatoiron(III)) ([(FePc^2?)₂O]) dissolved in pyridine reacts with different Tetra(n-butyl)ammonium salts yielding partly solvated Di(tetra(n-butyl)ammonium)-μ-oxodi(acidophthalocyaninatoferrates(III)) ((ⁿBu₄N)₂[(Fe(X)Pc^2?)₂O]; X^? = CN^?, Im^?, NCO^?, NCS^?, NO₂^?). The uv-vis. spectra show the typical B, Q, N and L regions of the Pc^2? ligand scarcely influenced by the axial ligands X. In comparison with [(FePc^2?)₂O] mainly the B region is hypsochromically shifted due to strong excitonic coupling (> 3 kK). Two regions of weak absorbance at ca. 7.6–8.7 and 11.4–13.0 kK are assigned to trip-doublet transitions. The m.i.r. and resonance Raman spectra are dominated by the fundamental vibrations of the Pc^2? ligand being characteristic for hexa-coordinated low-spin Fe^III phthalocyanines. Internal vibrations of the ambident axial ligands X are in accordance with the proposed Fe? X bond. The i.r. active asym. (Fe? O? Fe) stretching vibration is observed in the region 631–690 cm^?1. Fe? X stretching vibrations are only present in the f.i.r. spectra. The magnetic properties and Mößbauer spectra are interpreted in terms of an electronic model which assumes that a S′ = 1 ground state arises from strong ferromagnetic coupling of the low-spin Fe^III centres. Both spin-Hamiltonian and ligand-field models have been employed to fit the variable temperature susceptibility data. These low-spin μ-oxo Fe^III dimers are rare compared to the many known examples of coupled high-spin species including the parent, [(FePc^2?)₂O].     

Neue Rheniumkomplexe mit Trichalkogenido- und Tetrachalkogenido-Chelatliganden

New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate Ligands The reactions of Cp*ReCl₄ with polychalcogenide salts such as Na₂S₄ or (NEt₄)₂Se₆ lead initially to the violet trichalcogenido chelate complexes Cp*ReCl₂(E₃) (E = S ( 3a ), Se ( 3b )) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E₄) (E = S ( 4a ), Se ( 4b )) and Cp*Re(N^tBu)(E₄) (E = S ( 5a ), Se ( 5b )), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b–5b . It appears that the size of the Se^2?_n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

Chalkogenolat-lonen und ihre Derivate. I. Darstellung und Eigenschaften salzartiger Chalkogenophenolate

Chalcogenolates and their Derivatives. I. Syntheses and Properties of Ionic Chalcogenophenolates The syntheses and properties of ionic chalcogenophenolates are described. Using liquid ammonia as solvent the alkali chalcogenophenolates M[EPh] (M = Na, K; E = Se, Te; Ph = C₆H₅) have been synthesized via reduction of the diphenyl dichalcogenides with alkali metals. Similarly, the tetraphenylphosphonium chalcogenophenolates [Ph₄P][EPh] (E = S, Se, Te) have been obtained by reacting alkali chalcogenophenolates with tetraphenylphosphonium chloride.     

Tris(trimethylsilyl)methanselenenylhalogenide und -chalkogenide

Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides . Ditrisyldiselenide ( 1 ) (trisyl = TSi = (Me₃Si)₃C) reacts with SOCl₂, Br₂ and I₂ to provide trisylselenenyl halides TSiSeX ( 2 : X = Cl; 3 : X = Br, 4 : X = I). Insertion of S and Se into the Se? Se bond of 1 to yield (TSiSe)₂S_n ( 5 : n = 1; 6 : n = 2) and (TSiSe)₂Se_n ( 7 : n = 1; 8 : n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I₂ in CS₂ to give 4 and Se₂I₂ ( 9 ). From 2 with Me₃SiCN and Me₃SiNCS, the new selenenyl pseudohalides TSiSeCN ( 10 ) and TSiSeSCN ( 11 ) were prepared. The compounds were characterised by ¹H, ¹³C- and ⁷⁷Se n.m.r. spectra.     

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.     

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3– und trans‐[Rh(CN)2(SeCN)4]3–, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

Synthesis and Spectroscopic Characterization of [Rh(SeCN)₆]^3– and trans ‐[Rh(CN)₂(SeCN)₄]^3–, Crystal Structure of (Me₄N)₃[Rh(SeCN)₆] Treatment of RhCl₃ with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)₆]^3– and trans‐[Rh(CN)₂(SeCN)₄]^3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me₄N)₃[Rh(SeCN)₆] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me₄N)₃[Ir(SCN)₆]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu₄N)₃[Rh(SeCN)₆] ( 1 ) and trans‐(n‐Bu₄N)₃[Rh(CN)₂(SeCN)₄] ( 2 ) are in the range of 170–250 cm^–1. In 2 ν_as(CRhC) is observed at 479 cm^–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and f_d(RhC) = 3.14 mdyn/Å ( 2 ). f_d(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)₆]^3–, which has not been calculated so far. The ¹⁰³Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the ⁷⁷Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the ¹³C NMR spectrum at 136.3 ppm.     

Gitterschwingungsspektren. LXXI. Wasserstoffbrückenbindungen und synergetischer Effekt in kristallinen Amiden am Beispiel von NaAl(NH2)4

Lattice Vibration Spectra. LXXI Hydrogen Bonding and Synergetic Effect in Solid Amides: a Case Study for NaAl(NH₂)₄ IR and Raman spectra (4000 - 200 cm^?1, 90 K and 300 K) of NaAl(NH₂)₄ and of deuterated samples are recorded and discussed with respect to the bonding of NH₂^? ions in condensed phases compared to that of H₂O molecules and OH^?-ions. The bands observed are assigned to the internal vibrations and librations of the NH₂^? ions and skeleton vibrations of the distorted tetrahedral Al(NH₂)₄^? units (breathing vibration v₁, 572 cm^?1). Owing to the high charge density of the Al³⁺ ions the NH-stretching modes are shifted to higher wavenumbers by as many as 200 cm^?1 compared to those of free amide ions. Furthermore the H-bond donor strenght of the NH₂^? ions is so much enlarged (synergetic effect) that weak, unusally long (d( …? N) > 360 pm) NH₂ …? NH₂ hydrogen bonds are formed. These H-bonds share layers of vertex connected Al(NH₂)₄ and Na(NH₂)₄ tetrahedra within the structure.     

Die Kristallstruktur von Tris(N,N-Diethyl-N′ -benzoylthioureato) Rhodium(III)

Crystal Structure of Tris(N,N-Diethyl-N′-benzoylthioureato) Rhodium(III) Rh(C₁₂H₁₅N₂OS)₃ crystallizes in the trigonal space group P-3. The cell parameters are a = 16.660(2), c = 8.479(1) Å and Z = 2. The structure was solved with Patterson and direct methods and refined to a final R-value of 7.05%. Rh^III is octahedrally coordinated to three N,N-Diethyl-N′ -benzoylthiourea molecules, which are bidentately coordinated through their oxygen and sulfur atoms. The Rh? S and Rh? O bond lengths are 2.284 Å and 2.033 Å, respectively.