Mangan(IV)-Komplexe mit dreizähnigen diaciden Liganden. Kristallstruktur von Acetylacetonato-salicylaldehydbenzoylhydrazonato(2−)-methanol-mangan(III)

Manganese(IV) Complexes with Tridentate Diacidic Ligands. Crystal Structure of Acetyl-acetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) The manganese(IV) chelates of salicylaldehyde benzoylhydrazone and salicylaldehyde salicylhydrazone were synthesized by ligand exchange reactions using bis(acetylacetonato)manganese(II), tris(acetylacetonato)manganese(III) as well as manganese(III) acetate. The brown complexes show the expected molecular ions in the APCI mass spectra. As an intermediate compound acetyacetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) was isolated and characterized by X-ray structural analysis. Crystallographic data see “Inhaltsübersicht”.     

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).     

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.     

Ligandenaustauschreaktionen von Bis(acetylacetonato)dioxo-molybdän(VI). Kristallstrukturen von [Salicylaldehyd-benzoylhydrazonato(2–)]dioxo-methanol-molybdän(VI) und [Benzoylaceton-benzoylhydrazonato(2–)] dioxo-triphenylphosphanoxid-molybdän(VI)

Ligand Exchange Reactions of Bis(acetylacetonato)dioxo-molybdenum(VI). Crystal Structures of [Salicylaldehyde-benzoylhydrazonato(2–)]dioxo-methanol-molybdenum(VI) and [Benzoylacetone-benzoylhydrazonato(2–)]dioxo-triphenylphosphaneoxide-molybdenum(VI) The products of ligand exchange reactions between bis(acetylacetonato)dioxo-molybdenum(VI) and tridentate diacidic ligands H₂L in the presence of triphenylphosphane were found by mass spectrometry to be complexes of the type MoO₂L. In the case of salicylaldehyde 2-hydroxyanil MoL₂ could also be identified. The compounds MoO₂L were crystallized as complexes with methanol or triphenylphosphane oxide. Crystallographic data see “Inhaltsübersicht”.     

Template-Reaktion von Bis(acetylacetonato)-dioxo-molybdän(VI) mit Benzoylhydrazin und Triphenylphosphan

Template Reactions of Bis(acetylacetonato)-dioxo-molybdenum(VI) with Benzoylhydrazine and Triphenylphosphane By reaction of MoO₂(acac)₂ with C₆H₅? CO? NH? NH₂ in the presence of P(C₆H₅)₃ Mo(NNCOC₆H₅)((CH₃)₂CNNCOC₆H₅)(P(C₆H₅)) was obtained besides MoO(acac-NNHCOC₆H₅)(NNHCOC₆H₅). The earlier compound was characterized by X-ray structural analysis. Crystallographic data see ?Inhaltsübersicht”?.     

Struktur von Bis[salicylaldehyd-2-hydroxyanilato(2—)]vanadium(IV)

Molecular Structure of Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) By the reaction of tris(acetylacetonato)vanadium(III) with salicylaldehyde-2-hydroxyanil the non-oxo vanadium(IV) complex of this ligand was prepared. Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) has a distorted octahedral structure. Crystallographic data see “Inhaltsübersicht”.     

Synthese und Struktur von (NH4)2[(AuI4)(AuI2(μ2-I4))], einem Iodoaurat(III) mit I-Ionen als Liganden

Synthesis and Structure of (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))], a Iodoaurate(III) with I₄^2? Anions as Ligands (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))] is obtained in a sealed glass ampoule by slow cooling of a mixture of NH₄I, Au, and I₂ beforehand heated to 500°C. The compound forms black crystals decomposing slowly under loss of I₂. It crystallizes in the orthorhombic space group Pnma with a = 1357.7(1), b = 2169.9(2), c = 755.6(3) pm, and Z = 4. The crystal structure is built up by NH cations and square-planar [AuI₄]^? anions as well as [AuI₂(μ₂-I₄)]^? groups being linked together by the I ligands to form chains. The distances Au? I are in the range of 258.7(2) to 262.4(2) pm. The nearly linear I anions are characterized by a short central I? I distance of 270.9(3) pm and two longer outer distances of 338.7(2) pm.     

Polyol-Metall-Komplexe. X. Blei(II)-meso-oxolan-3,4-diolat(2−)-Monohydrat – ein polymeres Blei-alkoxid aus wäßriger Lösung

Polyol Metal Complexes. X. Lead(II) meso-Oxolane-3,4-diolate(2?) Monohydrate – a Polymeric Lead Alkoxide from Aqueous Solution In the colourless crystals of Pb(C₄H₆O₃) · H₂O (P2₁/c, a = 569.8(3), b = 607.6(4), c = 1856.9(9) pm, β = 89.90(4)°, V = 642.9(6) · 10⁶ pm³, Z = 4), lead(II)- and meso-oxolane-3,4-diolate(2?) ions form a one-dimensional coordination polymer; Pb^II is coordinated with four bridging alkoxide O-atoms (mean distance: 234.5 pm); some 100 pm more distant two μ-O-atoms of water molecules coordinate the lead ion.     

Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Oxofreie Vanadium(IV)-Komplexe mit dreizähnigen diaciden Liganden. Struktur von Bis[2,2′-dihydroxy-azobenzenato(2−)]vanadium(IV)

Non-oxo Vanadium(IV) Complexes with Tridentate Diacidic Ligands. Molecular Structure of Bis[2.2′-dihydroxy-azobenzenato(2?)]vanadium(IV) By the reaction of tris(acetylacetonato)vanadium(III) with tridentate diacidic ligands non-oxo vanadium(IV) complexes of these ligands were synthesized. The complexes were characterized by mass spectrometry. Electrochemical studies show that the complexes are reversibly oxidized or reduced. Bis[2,2′-dihydroxy-azobenzenato(2?)]vanadium(IV) has a distorted trigonal-prismatic structure. Crystallographic data see ?Inhaltsübersicht”?.     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

1‐Oxa‐nido‐dodecaborate [OB11H12]− from the Controlled Oxidation of the closo‐Borates [B11H11]2− and [B12H12]2−

The closo‐dodecaborate [B₁₂H₁₂]^2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)₃. The degradation is induced by Ag²⁺ ions, generated from Ag⁺ by the action of H₂S₂O₈. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt₃][OB₁₁H₁₂] after five days in a yield of 18 %. The action of FeCl₃ on the closo‐undecaborate [B₁₁H₁₁]^2? in an aqueous solution gives either [B₂₂H₂₂]^2? (by fusion) or nido‐B₁₁H₁₃(OH)^? (by protonation and hydration), depending on the concentration of FeCl₃. In acetonitrile, however, [B₁₁H₁₁]^2? is transformed into [OB₁₁H₁₂]^? by Fe³⁺ and oxygen. The radical anions [B₁₂H₁₂] ^{˙ ?} and [B₁₁H₁₁] ^{˙ ?} are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag²⁺ and Fe³⁺, respectively. These radical anions are subsequently transformed into [OB₁₁H₁₂]^? by oxygen. The crystal structure analysis shows that the structure of [OB₁₁H₁₂]^? is derived from the hypothetical closo‐oxaborane OB₁₂H₁₂ by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory.     

Synthesis and structural characterisation of the oxo-rhenium(V) complexes with spirophosphorane derived bidentate ligand (PO). Crystal structure of trans-ReOCl2[OCMe2CMe2OP(OCMe2CMe2O)](PPh3)

The reactions of ReO(OEt)Cl₂L₂, L=py, PPh₃ or ReOCl₃(Me₂S)(OPPh₃), with spirohydrophosphorane HP(OCMe₂CMe₂O)₂ – abbreviated here as HPO – in toluene yield ReOCl₂(PO)L complexes, L=py (1), PPh₃ (2) and OPPh₃ (3), respectively. The encountered bidentate phosphite pinacolato (OCMe₂CMe₂O)POCMe₂CMe₂O⁻ ligand (PO⁻) is afforded by means of a spirophosphorane ring-opening reaction. All the pink–violet compounds 1–3 were characterised by NMR, IR and UV–Vis spectroscopies. The structure of trans-ReOCl₂(PO)PPh₃ (2) was determined crystallographically. The rhenium atom adopts distorted octahedral geometry with a trans multiply bonded terminal oxo ligand (Re–O_t=1.698(2) Å) trans to pinacolate oxygen (Re–O=1.880(2) Å). Two phosphorus atoms as well as two chlorides are mutually in a trans arrangement.     

Enantioselective Synthesis of (−)‐(R)‐Cordiachromene and (−)‐(R)‐Dictyochromenol Utilizing Intramolecular SNAr Reaction

A simple and efficient enantioselective synthesis of chromene, (?)‐(R)‐cordiachromene ( 1 ), and (?)‐(R)‐dictyochromenol ( 2 ) has been accomplished. This convergent synthesis utilizes intramolecular S_NAr reaction for the formation of chroman ring, and Seebach's method of ‘self‐reproduction of chirality’ should establish the (R)‐configuration of the C(2) side chain as key steps.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.     

Synthese und Struktur des Kupferkomplexes 2-(2-Hydroxy-5-methylphenyl)-6-(2-hydroxyphenyl)pyridinato(2−)-dipyridin-kupfer(II) und des freien Liganden

Synthesis and Structure of the Copper Complex 2-(2-Hydroxy-5-methylphenyl)-6-(2-hydroxyphenyl)pyridinato(2?)dipyridin-copper(II) and of the free Ligand The tridentate diacidic ligand 2-(2-hydroxy-5-methyl)-6-phenyl-6-(2-hydroxyphenyl)pyridine 4a was synthesized and characterized by X-ray structural analysis. The compound forms a copper complex, 2-(2-Hydroxy-5-methyl-phenyl)-6-(2-hydroxyphenyl)pyridinato(2?)-dipyridine copper(II), which was crystallized from pyridine solution. The coordination number of the central atom copper ist five.     

19F-NMR-spektroskopischer Nachweis und statistische Untersuchung zur Bildung der gemischten Clusteranionen [(Mo6ICl)F]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I)F]

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆I Cl )F ]^2?, n = 0–7, and Preparation of (TBA)₂[(Mo₆I )F ] The octa-μ₃-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo₆I)F]^2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo₆ICl)⁴⁺, n = 0–7 is formed by exchange of innersphere bound Clⁱ against outersphere bound I^a on tempering solid [(Mo₆Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)₂[(Mo₆ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 ¹⁹F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-¹⁹F/¹⁹F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.     

Crystallographic report: A two‐dimensional homochiral coordination polymer: [cadmium(II) bis(S‐(−)‐lactate)]n

In the two‐dimensional (2D) homochiral structure of [cadmium(II) bis(S‐(?)‐lactate)]_n, the lactate ligand adopts a µ₃‐bridging mode to connect two cadmium atoms, leading to the formation of a 2D network. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

(PPh4)[(ReO2S2)CuI] und (NEt4)2[(ReOS3)Cu3Cl4]: Fixierung der bisher nicht isolierten Ionen [ReO2S2]− und [ReOS3]− durch Ausnutzung der Stabilität der CuS2(Re)- und Cu3S3(Re)-Fragmente

(PPh₄)[(ReO₂S₂)CuI] and (NEt₄)₂[ReOS₃)Cu₃Cl₄]: Fixation of the up to now not Isolated Ions [ReO₂S₂]^? and [ReOS₃]^? Utilizing the Stability of the CuS₂(Re) and Cu₃S₃(Re) Fragments (PPh₄)[(ReO₂S₂)CuI] ( 1 ) and (NEt₄)₂[ReOS₃)Cu₃Cl₄] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO₂S₂]^? and [ReOS₃]^? as ligands, have been prepared by the reaction of (NEt₄)[ReS₄] with PPh₃ and CuI in acetone in the presence of (PPh₄)I (( 1 )) or with CuCl in CH₂Cl₂ in the presence of (NEt₄)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht.