Chemie polyfunktioneller Moleküle. 116. Hydrido-, Deuterido-, Thiolato- und Chlororuthenium(II)-Komplexe des Bis(diphenylphosphino)amins

Chemistry of Polyfunctional Molecules. 116 Hydrido-, Deuterido-, Thiolato-, and Chlororuthenium(II) Complexes of Bis(diphenylphosphino)amine Bis(diphenylphosphino)amine, [(C₆H₅)₂P]₂NH (dppa, 1 ), reacts with [Ru(cod)(cot)] (cod = η-1,5-cyclooctadiene, cot = η-1,3,5-cyclooctatriene) ( 2 ) in a molar ratio of 2 : 1 both in a hydrogen or deuterium atmosphere at room temperature to yield cis-[Ru(H)₂(dppa)₂] ( 3 ) and cis-[Ru(D)₂(dppa)₂] ( 3 a ), respectively. The dihydride complex 3 is very sensitive towards halogenated solvents: dissolution of 3 in CHCl₃ or CH₂Cl₂ produces the monohydride compound trans-[RuCl(H)(dppa)₂] ( 4 ). Treatment of 3 with a threefold excess of tert-butyl mercaptane, Me₃CSH, at room temperature results in the formation of cis-[Ru(H)(SCMe₃)(dppa)₂] ( 5 ). Trans-[RuCl₂(dppa)₂] ( 7 ) can be synthesized by the interaction of [RuCl₂(PPh₃)₃] ( 6 ) with one or two equivalents of 1 in CH₂Cl₂ solution. The NMR spectra of 3, 3 a, 4, 5 and 7 are discussed with respect to molecular stereochemistry and hydrogen-halogen exchange under simultaneous cis-trans rearrangement. In addition to ¹H, ²H, ³¹P{¹H}, and ³¹P NMR, the structures of the different complexes were also derived from 1R, Raman, and mass spectra. The NMR spectra simulation of 3 permits detailed assignments of spin-spin coupling constants. Crystals of cis-[Ru(H)(SCMe₃)(dppa)₂] ( 5 ) are monoclinic, space group P2₁/c, with a = 1 179.9(3), b = 2 228.0(4), c = 1 854.8(6) pm, β = 96.23(2)°, Z = 4, and R_w = 0.062. The structural analysis shows that ruthenium is coordinated by two bidentate organophosphine ligands and by one tert-butyl thiolate molecule. The metal bound hydrogen atom was not located. However, in agreement with ¹H NMR, its position is trans to a phosphorus nucleus.     

Chemie polyfunktioneller Moleküle. 124. Silber(I)-Komplexe mit den Liganden Bis(diphenylphosphanyl)amin, -amid und Tris(diphenylphosphanyl)amin

Chemistry of Polyfunctional Molecules. 124. Silver(I) Complexes Containing the Ligands Bis(diphenylphosphanyl)amine, -amide and Tris(diphenylphosphanyl)amine Bis(diphenylphosphanyl)amine HN(PPh₂)₂ ( 1 ) reacts with AgCl to the complex HN(PPh₂AgCl)₂ ( 5 ) for which in the solid state the cluster structure Ag₄Cl₄[HN(PPh₂)₂]₂ is assumed. Reaction of 5 with LiN(PPh₂)₂ ( 2 ) gives the known [N(PPh₂AgPh₂P)₂N] ( 8 ) and the new complex [Ag(μ—Ph₂PNPPh₂)₂(μ—Ph₂PNHPPh₂)Ag] · dioxane ( 7 · dioxane). The compound 7 · dioxane has been characterized by X-ray diffraction. The molecules are found to contain a bicyclo[3.3.3]undecane-type structure with trigonal planar coordinated silver atoms, which are separated by 281,6(1) pm. The dioxane is bound via H-bridge bond to the NH group of the coordinated HN(PPh₂)₂. Treatment of 8 with ClPPh₂ yields N(PPh₂AgCl)₃ ( 12 ), which has also been obtained by the reaction of N(PPh₂)₃ ( 3 ) with silver chloride. All the compounds have been characterized, so far as possible, by IR, Raman, ¹H NMR, ³¹P{¹H} NMR, ¹³C{¹H} NMR and mass spectroscopy.     

Neue Alkylchlorsulfonium-Salze und Kristallstruktur von Diethylchlorsulfoni-umhexachloroantimonat (C2H5)2SCl+SbCl6−

New Alkylchlorosulfonium Salts and Crystal Structure of Diethylchlorosulfonium-Hexachloroantimonate (C₂H₅)₂SCl⁺SbCl₆^? We describe the preparation and spectroscopic characterization of Dialkylchlorosulfonium-Hexachloroantimonates R₂SCl⁺SbCl₆^? (R = C₂H₅, i-C₃H₇) and the crystal structure of Diethylchlorosulfonium-Hexachloroantimonate (C₂H₅)₂SCl⁺SbCl₆^? at 172(1) K. The salt crystallize in the orthorhombic space group P2₁2₁2₁ with a = 980.4(13) pm, b = 1010.6(8) pm, c = 1492.8(14) pm with four formula units per unit cell.     

Chemie polyfunktioneller Moleküle. 101 [1]: Synthese eines Diphenylphosphin-substituierten Cyclophosphamide und Röntgenstrukturanalyse seines Oxidations-produkts

Inhaltsübersicht. Diphenylphosphin und rac-Cyclophosphamid (ClCH₂CH₂)₂NP(O)N(H)(CH₂)₃O (1) reagieren in Gegenwart von n-Butyllithium zu einem Zwischenprodukt, das mit Wasser das diphenylphosphinsubstituierte Cyclophosphamid, (Ph₂PCH₂CH₂)₂NP(O)N(H)(CH₂)₃O, (2) bildet. Metallierung von 2 mit n-BuLi am N(3)-Atom und Umsetzung mit D₂O führt zum N(3)-Deuteroderivat 2a. Mit H₂O₂ reagiert 2 zur all-Phosphinoxid Verbindung, [Ph₂P(O)CH₂CH₂]₂NP(O)N(H)(CH₂)₃O, (4), die mit 0,5 Mol Wasser auskristallisiert und von der zur Charakterisierung des H-Bückenbindungssystems eine Röntgenstrukturanalyse angefertigt wurde. Die NMR-Spektren (¹H, ¹³C, ³¹P, ¹⁴N) weisen 2–4 als dynamische Moleküle aus. Chemistry of Polyfunctional Molecules. 101. Synthesis of a Diphenylphosphinesubstituted Cyclophosphamide and the X-ray Diffraction of its Oxidation Product Diphenylphosphine and rac-cyclophosphamide, (ClCH₂CH₂)₂NP(O)N(H)(CH₂)₃O, (1) react in the presence of n-BuLi to an intermediate which hydrolyses to the diphenylphosphine substituted Cyclophosphamide, (Ph₂PCH₃CH₂)₂NP(O)N(H)(CH₂)₃O, (2). Metallation of 2 with n-BuLi at the N(3) atom, followed by treatment with D₂O yields the N(3)-deuterated derivative 2a. With H₂O₂ 2 forms the all-phosphine-oxide compound, [Ph₂P(O)CH₂CH₂]₂NP(O)N(H)(CH₂)₃O, ( 4 ), which crystallizes with 0.5 mole of water. In order to characterize the H-bridge bonding system a X-ray structure analysis of 4 was carried out. The NMR-Spectra (¹H, ¹³C, ³¹P, ¹⁴N) indicate 2–4 as dynamic molecules.     

Pseudoelementverbindungen. VII [1]. Kristall- und Molekülstruktur von Tris(ethylendiamin)nickel(II)-bis(2-methyl-4-chlorphenoxycyanamidoacetat)

Pseudoelement Compounds VII. [1] Crystal and Molecular Structure of Tris(ethylenediamine)nickel(II)-bis(2-methyl-4-chlorophenoxy-cyanamidoacetate) Surprisingly, in the presence of ethylenediamine 2-methyl-4-chlorphenoxy-cyanamidoactetate reacts with nickel(II) and copper(II) ions preferentially under formation of complexes of the type [M(en)₃]X₂. The IR spectra and the X-ray diffraction investigations corresponding to [Ni(en)₃][2-Me-ClC₆H₃OCH₂C(O)NCN]₂ show that two cyanamidocarboxylate ions [RC(O)NCN]^? are bonded to the complex cation through, in each case, two N? H …? O?C hydrogen bonds between NH protons of ethylenediamine ligands and the carbonyl oxygen atoms. Additionally, in the crystal weak N? H …? N?C bridges were found between the nitrile nitrogen atoms of the anions and NH protons of neighbouring complex cations.     

Chemie polyfunktioneller Moleküle, 126 Mitt. Synthese, Struktur und Tautomerie von 5-Fluor-N(1), N(3)-bis(diphenylphosphanyl)-uracil

Summary 5-Fluoro-uracil (1) reacts with chloro-diphenylphosphane to 5-fluoro-N(1), N(3)-bis(diphenylphosphanyl)uracil (3) which was characterized by X-ray crystallography, IR, and mass spectra.¹⁹F,³¹P{¹H},¹³C{¹H}, and¹H NMR spectra indicate that3 rearranges inTHF solution to some extent to the tautomeric 5-fluoro-O(2), O(4)-bis(diphenylphosphanyl)uracil (4). If the solvent contains traces of water, Ph₂P(O)-PPh₂ (6) and uracil derivatives are formed by hydrolysis.

Herrn Professor Dr.Walter Siebert zum 60. Geburtstag gewidmet.     

Chemie polyfunktioneller Moleküle. 119 [1] Tetracarbonyl-dicobalt-tetrahedran-Komplexe mit den Liganden Bis(diphenyl-phosphanyl)amin, 2-Butin-1,4-diol und tert-Butylphosphaacetylen — Kristallstrukturanalyse des Phosphaalkin-Derivats

Chemistry of Polyfunctional Molecules. 119 [1]. Tetracarbonyl-dicobalt-tetrahedrane Complexes with the Ligands Bis(diphenylphosphanyl)-amine, 2-Butin-1,4-diol, and tert.-Butylphosphaacetylene — Crystal Structure of the Phosphaalkyne Derivative Co₂(μ-CO)₂(CO)₄(μ-Ph₂P? NH? PPh₂—P,P′) · 1/2C₆H₅CH₃ ( 4 · 1/2C₆H₅CH₃) reacts with 2-butine-1,4-diol, HOCH₂? C?C? CH₂OH ( 5 ), to the dark-red tetrahedrane complex Co₂(CO)₄(μ-η²,η²-HOCH₂? C?C? CH₂OH? C², C³) · (μ-Ph₂P? NH? PPh₂? P,P′) · THF (6 · THF). With t-butyl-phosphaacetylene, tBu? C?P ( 7 ), 4 · THF forms Co₂(CO)₄(μ-η²,η²-tBu? C?P)(μ-Ph₂P? NH? PPh₂? P,P′) ( 8 ), which also belongs to the tetrahydrane type. The compounds were characterized by their mass, IR, ³¹P{¹H} NMR, ¹³C{¹H} NMR, and¹H NMR spectra. Crystals suitable for X-ray structure analyses have been obtained for 8 from dioxane. The dark red blocks crystallize in the monoclinic P2₁/c space group with the lattice constants a = 1404,1(5), b = 1330,0(7), c = 2578,8(10)pm; β = 90,82(3)°.     

Chemie polyfunktioneller Moleküle. 103 [1]: Chrom-, Molybdän- und Wolframtetra- sowie -tricarbonyl-Komplexe eines Diphenylphosphin-substituierten Cyclophosphamide

Inhaltsübersicht. (Ph₂PCH₂CH₂)₂N-P(O)N(H)CH₂CH₂CH₂O ( 2 ) bildet mit cis-M(CO)₄(C₇H₈) bzw. fac-M(CO)₃(CH₃CN)₃ (M = Cr, Mo, W; C₇H₈ = Norbornadien) die Chelat-komplexe cis-M(CO)₄(PPh₂CH₂CH₂)₂N-P(O)N(H)CH₂CH₂CH₂O ( 3a–c ) bzw. fac-M(CO)₃(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O ( 4a–c ). 3a kristallisiert mit einem Mol Methanol aus, während 4a–c jeweils ein halbes Mol THF als Solvat enthalten. Alle Verbindungen wurden, soweit möglich, durch IR-, Raman-, ¹H-NMR-, ³¹P-NMR-, ¹³C-NMR- und Massenspektren charakterisiert. Chemistry of Polyfunctional Molecules. 103. Chromium, Molybdenum, and Tungsten Tetra- and Tricarbonyl Complexes of a Diphenylphosphine-substituted Cyclophosphamide Abstract. (Ph₂PCH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O (2) forms with cis-M(CO)₄(C₇H₈) or fac-M(CO)₃(CH₃CN)₃ (M = Cr, Mo, W; C₇H₈ = norbornadiene) the chelate complexes cis-M(CO)₄(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₃O ( 3a–c ) or fac-M(CO)₃(PPh₂CH₂CH₂)₂N–P(O)N(H)CH₂CH₂CH₂O ( 4a–c ). 3a crystallizes with one mole of methanol whereas 4a–c contain 1/2 mole of THP as solvate. All compounds were, as far as possible, characterized by their IR, Raman, ¹H NMR, ³¹P NMR, ¹³C NMR, and mass spectra.     

Chemie polyfunktioneller Moleküle, 94 Chrom- und Wolfram-pentacarbonylderivate des 4-Methyl-1,2,6-triphosphatricyclo[2.2.1.02,6]heptans (P3-Nortricyclans)

The P₃-nortricyclane 4-methyl-1,2,6-triphosphatricyclo[2.2.1.0^2,6]heptane, CH₃C(CH₂P)₃, (1), is synthesized in a better yield than earlier described from P₄, a Na/K alloy, and CH₃C(CH₂Br)₃ in boiling 1,2-dimethoxyethane. It reacts withM(CO)₅ thf (M=Cr, W) in the molar ratios of 1:1, 1:2, and 1:3 to form the pentacarbonylmetal complexes CH₃C(CH₂P)₃[M(CO)₅] _n [n=1, 2, 3;M=Cr (a), W (b)], (2 a, b–4 a, b).1 gives with Mo(CO)₅ thf only mixtures of CH₃C(CH₂P)₃[Mo(CO)₅] _n andcis-Mo(CO)₄ derivatives, which were identified by their infrared active A₁ v(CO) modes at 2075 and 2025 cm^–1.All the new compounds have been characterized also by their¹H{³¹P},³¹P{¹H} NMR, IR,Raman, and mass spectra.

     

Beiträge zur Kristallchemie und zum thermischen Verhalten von wasserfreien Phosphaten. XXXVI [1] Synthese,Kristallstruktur und spektroskopische Charakterisierung von Palladium(II)‐diphosphat Pd2P2O7

Synthesis, Crystal Structure and Spectroscopical Characterization of Palladium(II)‐Diphosphate Pd₂P₂O₇ Pd₂P₂O₇ is synthesized by heating (T_max = 500 °C) stoichiometric amounts of PdO and phosphoric acid. Using chemical vapour transport experiments (850 °C → 750 °C, addition of PdCl₂) Pd₂P₂O₇ was crystallized. Pd₂P₂O₇ adopts its own structure type (C 2/c (No. 15), Z = 4, a = 13,151(2) Å, b = 5,172(1) Å, c = 8,139(1) Å, β = 97,52(1)°, 1160 independent reflections, 55 variables, R1 = 0,021 and wR2 = 0,050). Square‐planar [PdO₄]‐units are linked by diphosphate‐groups generating a 3D framework. Within this framework ribbons may be distinguished. Thus Pd₂P₂O₇ might be described as palladium(II)‐[diphosphatopalladate(II)]. The results of various spectroscopic measurements (IR, Raman, UV/VIS, ³¹P‐MAS‐NMR) are reported and discussed within the context of the crystal structure.     

Beiträge zur Chemie des Siliciums und Germaniums. XXXIII [1]. Zur Darstellung von Kaliumsilyl

Reines, monoglyme- und kaliumhydridfreies, kristallines Kaliumsilyl wird aus Monosilan und Na/K-Legierung in Monoglyme unter Anwendung einer speziellen Art der Dosierung von Monosilan erhalten. Die analytische Charakterisierung der Verbindung ist durch Hydrolyse sowie durch Umsetzung mit Benzylchlorid und nachfolgende gaschromatographische Untersuchung des Reaktionsproduktes möglich. Löslichkeitsuntersuchungen von Kaliumsilyl in verschiedenen Solventien haben in Monoglyme eine zunehmende Löslichkeit mit abnehmender Temperatur ergeben. Die Leitfähigkeit einer Lösung von Kaliumsilyl in Monoglyme ist gemessen worden. Contributions to the Chemistry of Silicon and Germanium. XXXIII. On the Preparation of Potassium Silyl Pure, crystalline potassium silyl, free of glyme and potassium hydride, is prepared from monosilane and Na/K alloy, using a special method of dosing the monosilane. The substance was characterized by hydrolysis and by gaschromatographic investigation of the products from its reaction with benzyl chloride. Studying the solubility of potassium silyl in different solvents an increasing solubility in glyme is observed while the temperature is lowered. The conductivity of a solution of potassium silyl in glyme has been measured.     

Über Chalkogenolate. 206 [1]. N-Thioacetyldithiocarbamate und Ester der N-Thioacetyldithiocarbamidsäure

On Chalcogenolates. 206. N-Thioacetyl Dithiocarbamates and Esters of N-Thioacetyl Dithiocarbamic Acid Thioacetamide reacts with carbon disulfide in the presence of KH to form via the tetrabutyl ammonium salt dark yellow N-thioacetyl dithiocarbamates M[S₂C? NH? CS? CH₃], where M = K, Rb, Cs. The salts as well as the methyl and ethyl ester have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioacetyl dithiocarbamic acid were not successful.     

1,4-Dihydro-1λ5,4λ5-[1,4]diphosphinine und ein 1,4-Dihydro-1λ3,4λ3-[1,4]diphosphinin

1,4-Dihydro-1λ⁵,4λ⁵-[1,4]diphosphinines and a 1,4-Dihydro-1λ³,4λ³-[1,4]diphosphinine Reaction of thio- or dithiocarbonic acids with ethinyl amino phosphanes leads to 1,4-dihydro-1λ⁵,4λ⁵-[1,4]diphosphinine-1,4-disulfides. By this route compounds 4, 7 , and 8 have been prepared. Desulfurization of 4 with tri-n-butylphosphane results in 1,2,4,5-tetraphenyl-1,4-dihydro-1λ³,4λ³-[1,4]-diphosphinine 5 , which can be oxidized with tert-butyl-peroxide to the corresponding dioxide, 6 . From the reaction mixture of phenyl-phenylethinyl diethylamino phosphane and thioacetamide compound 4 and the unsymmetrical 1,4-dihydro-1λ⁵,4λ⁵-[1,4]diphosphinine 9 were isolated. Properties, nmr, ir and mass spectra of all new products are reported. A mechanism for the formation of 9 is suggested. The results of the X-ray structure determination of 8 and 9 are described.     

Synthese und Kristallstruktur von Alkalimetalldiamidodioxosilicaten M2SiO2(NH2)2 mit M ≙ K,Rb und Cs

Synthesis and Crystal Structure of Alkali Metal Diamido Dioxosilicates M₂SiO₂(NH₂)₂ with M ? K, Rb and Cs SiO₂ – α-quartz – reacts with alkali metal amides MNH₂ (M ? K, Rb, and Cs) in molar ratios from 1:2 to 1:10 at 450°C ≤ T ≤ 600°C and P(NH₃) = 6 kbar in autoclaves to diamidodioxosilicates M[SiO₂(NH₂)₂]. Crystals of the colourless compounds which hydrolyze rapidly were investigated by x-ray methods. Following data characterize the structure determination on the isotypic compounds: The structures of the diamidodioxosilicates are closely related to the β? K₂SO₄ type. They contain isolated [SiO₂(NH₂)₂]^2? ions. K⁺ ions and hydrogen bridge bonds N? H…?O (with 2.68 Å ≤ d(N…?O) ≤ 2.78 Å for the K compound) connect the tetrahedral anions.     

Chemie polyfunktioneller Moleküle. 93. Die halogenierende Ringspaltung des As3-Nortricyclans, 4-Methyl-1,2,6-triarsatricyclo[2.2.1.02,6]heptan Darstellung und Eigenschaften von 2,6-Dihalogen-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanen

Chemistry of Polyfunctional Molecules. 93. Halogenating Ring Cleavage of As₃-Nortricyclane 4-Methyl-1,2,6-triarsatricyclo[2.2.1.0^2,6]heptane. Preparation and Properties of 2,6-Dihalogeno-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanes The reaction of the As₃-nortricyclane CH₃C(CH₂As)₃ ( 1 ) with PCl₅, Br₂, or I₂ in a molar ratio of 1:1 leads to the new 2,6-dihalogeno-4-methyl-1,2,6-triarsabicyclo[2.2.1]heptanes CH₃C(CH₂As)₃X₂ (X = Cl, Br, I; 2a–c ). Application of a molar ratio of 1:2 results in the formation of 1,1,1-tris(dihalogenoarsinomethyl)ethanes CH₃C(CH₂AsX₂)₃ ( 4a–c ) in rather poor yields; ¹H-NMR spectroscopic studies suggest that 4a–c are formed via 2a–c and the tetrahalogenodiarsacyclopentane derivatives ( 3a–c ); the latter can not be isolated from their solutions. 4a–c are obtained in very good yields by treatment of 1 with the halogenating agents in a molar ratio of 1:3 Comproportionation of 1 with 4a–c (molar ratio of 2:1) gives also 2a–c . Whereas in CD₂Cl₂ or CS₂ disproportionation of 2a leads to an equilibrium between 1 and 4a , which is formed via the intermediate 3a . The homologues 2b, c are stable with respect to disproportionation in both solvents.     

Über Chalkogenolate. 204. Reaktion von Acetamid mit Kohlenstoffdisulfid. 1. Darstellung und Eigenschaften von N-Acetyldithiocarbamaten

On Chalcogenolates. 204. Reaction of Acetamide with Carbon Disulfide. 1. Synthesis and Properties of N-Acetyl Dithiocarbamates Acetamide reacts with carbon disulfide in the presence of a strong base to form via the tetrabutyl ammonium salt the N-acetyl dithiocarbamates M[S₂C? NH? CO? CH₃] with M = Na, K, Rb, Cs, [N(ⁿC₄H₉)₄]. The new compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-acetyl dithiocarbamic acid were not successful.     

Zur Chemie des Dimesityleisens. IX [1]. Diaryleisen-Komplexe der Koordinationszahl drei und vier: Kristallstrukturen von [FeMes2(col)] (Mes = 2,4,6-Trimethylphenyl,col = 2,4,6-Trimethylpyridin) und [FeTrip2(py)2] (Trip = 2,4,6-Triisopropylphenyl,py = Pyridin)

Chemistry of Dimesityl Iron. IX. Diaryl-Iron Complexes with Coordination Number Three and Four: Crystal Structures of [FeMes₂(col)] and [FeTrip₂(py)₂] The diaryliron compounds FeMes₂, 1 , and FeTrip₂, 2 , from complexes with coordination numbers (CN) of four, normally. Bulky ligands however give adducts with CN of three. The crystal structures of compounds [ 1 (col)] (CN 3) and [ 2 (py₂)] (CN 4) have been determined.     

Synthese und Eigenschaften von Eisen(II)-Komplexen mit vier- und fünfzähnigen N,S-Chelatliganden. Kristallstruktur von [Fe(GBMA)py] · py (GBMA2− = Glyoxal-bis-(2-mercaptoanil))

Synthesis and Properties of Iron(II) Complexes with tetra- and pentadentate N,S-Chelate Ligands. Crystal Structure of [Fe(GBMA)py] · py (GBMA^2? = Glyoxal bis-(2-mercaptoanil)) The complexes glyoxal-bis-(2-mercaptoanil)iron(II) [Fe(GBMA)], diacetyl-bis-(2-mercaptoanil)iron(II), [Fe(DBMA)] and o-phthalaldehyde-bis-(2-mercaptoanil)iron(II) [Fe(PhBMA)] have been synthesized by reaction of the corresponding protonated ligands with anhydrous iron(II)-acetate. Pyridine-2,6-dialdehyde-bis-(2-mercaptoanil)iron(II), [Fe(PyBMA)] was obtained by a template synthesis with pyridine-2,6-dialdehyde, 2-aminothiophenol and iron(II)-acetate. Recrystallizing the complexes [Fe(GBMA)] and [Fe(DBMA)] from pyridine afforded [Fe(GBMA)py] · py and [Fe(DBMA)py] · py. For all complexes the magnetic properties have been determined, and the Mössbauer spectra were recorded at 82 K. Compounds [Fe(GBMA)] and [Fe(DBMA)] show quasi reversible redox properties in the cyclovoltammogram, while for [Fe(PhBMA)] an irreversible oxidation was observed. [Fe(GBMA)py] · py crystallizes in the monoclinic space group P2₁ with a = 1288.7(1), b = 1242.63(5), c = 1396.0(1) pm, β = 98.24(1)°, and Z = 4. In the neutral complex the Fe atom has a square pyramidal coordination with the pyridine nitrogen atom in apical position. The basal plane is formed by two nitrogen and two sulfur atoms of the ligand GBMA^2?. The iron is located 40 pm above the pyramidal base. Its average distances to the donor atoms of the GBMA ligand are Fe? N = 190 pm, and Fe? S = 222 pm, while the distance to the nitrogen atom of the coordinated pyridine molecule is 207 pm.     

Vanadium-Komplexe mit dreizähnigen diaciden Liganden. Die Kristallstrukturen von Bis[acetylacetonthiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehydthiobenzoylhydrazonato(2-)]vanadium(V) und Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanolvanadium(V)

Vanadium Complexes with Tridentate Diacidic Ligands. The Crystal Structures of Bis[acetylacetonato-thiobenzoylhydrazonato(2-)]vanadium(IV), Methoxo-oxo-[salicylaldehyd-thiobenzoylhydrazonato(2-)]vanadium(V), and Methoxo-oxo-[salicylaldehydbenzoylhydrazonato(2-)]methanol Vanadium(V) By template reactions of bis(acetylacetonato)oxovanadium(IV) and bis(salicylaldehydato)oxo-vanadium(IV), respectively, with benzoylhydrazine, thiobenzoylhydrazine, and 2-aminophenol the vanadium(IV) complexes V(LLL)₂ of tridentate azomethine ligands LLL were synthesized. The complexes were characterized by EPR spectroscopy and by absorption spectroscopy. From the complex V(LLL)₂ ( 1 ), in which LLL is acetyl-aceton-thiobenzoydrazonate(2-), the crystal structure analysis was solved. The vanadium atom in 1 is coordinated trigonal-prismatically by two N, 0 and S atoms. Furthermore, the 0x0 vanadium(V) complexes[VO(LLL)(OCH,)] (6) with LLL = salicylaldehyd-thio-benzoylhydrazonato(2-) and [VO(LLL)(OCH₃)· -CH₃OH] (7) with LLL = salicylaldehydbenzoylhydrazonato(2-) were identified by X-ray diffraction and by IR spectroscopy in the reaction products. Crystallographic data for 1, 6 , and 7 see ?Inhaltsübersicht”?.     

Synthesen und Schwingungsspektren der homoleptischen Acetonitrilkomplex-Kationen [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+ und des Adduktes CH3CN · SbF5. Kristallstrukturen der Salze [M(NCCH3)4][SbF6]2 · CH3CN,M = Pd,Pt

The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH₃)₂]⁺, [Pd(NCCH₃)₄]²⁺, [Pt(NCCH₃)₄]²⁺, and the Adduct CH₃CN · SbF₅. The Crystal and Molecular Structures of [M(NCCH₃)₄][SbF₆]₂ · CH₃CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)₄][Sb₂F₁₁]₂, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb₂F₁₁]^– into [SbF₆]^– and the molecular adduct CH₃CN · SbF₅ according to: [M(CO)₄][Sb₂F₁₁]₂ + 7 CH₃CN → [M(NCCH₃)₄][SbF₆]₂ · CH₃CN + 2 CH₃CN · SbF₅ + 4 CO M = Pd, Pt The monosolvated [M(NCCH₃)₄][SbF₆]₂ · CH₃CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH₃)₂][SbF₆] and the adduct CH₃CN · SbF₅ are completely characterized by vibrational spectroscopy.