Ligandverhalten von P‐funktionellen Organozinnhalogeniden: Nickel(II)‐, Palladium(II)‐ und Platin(II)‐halogenid‐Komplexe mit Me2(Cl)SnCH2CH2PPh2

Ligand Behaviour of P‐functional Organotin Halides: Nickel(II), Palladium(II), and Platinum(II) Complexes with Me₂(Cl)SnCH₂CH₂PPh₂ Me₂(Cl)SnCH₂CH₂PPh₂ ( 1 ) reacts with Ni^II, Pd^II, and Pt^II halides in molar ratio 2 : 1 forming the complexes [MX₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] (M = Ni, Pd, Pt; X = Cl, Br) ( 3 – 6 , 9 , 10 ) ( 7 , 8 : M = Ni; Br instead of Cl). The nickel complexes were isolated and characterized both as the planar ( 3 , 5 , 7 ) and the tetrahedral ( 4 , 6 , 8 ) isomer. Crystal structure analyses and NMR data indicate for the planar nickel complexes 3 , 5 , 7 and [MCl₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 9 : M = Pd; 10 : M = Pt) the existence of intra and intermolecular M–Hal…Sn bridges. In a ligand : metal molar ratio of 3 : 1 the complexes [M^éCl{PPh₂CH₂CH₂Sn^⊖Cl₂Me₂}{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 11 : M = Pd; 12 : M = Pt) are formed which represent intramolecular ion pairs. By dehalogenation of [PdCl₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 9 ) with sodium amalgam and graphite potassium (C₈K), respectively, the palladacycles cis‐[Pd{PPh₂CH₂CH₂SnMe₂}₂] ( 13 ) and trans‐[Pd(Cl)PPh₂CH₂CH₂SnMe₂{PPh₂CH₂CH₂Sn(Cl)Me₂}] ( 14 ) are formed. From the compounds 1 , 3 , 9 , 11 , and 12 the crystal structures are determined. All compounds are characterized by ¹H, ³¹P, and ¹¹⁹Sn NMR spectroscopy.     

Zum Koordinationsverhalten der Phenylhydrazonpropandinitrile: Darstellung und strukturelle Charakterisierung von Silber(I)‐Komplexen

On the Coordination Behaviour of Phenylhydrazonepropanedinitriles: Preparation and Structural Characterization of Silver(I) Complexes The preparation of novel silver(I) complexes with anions of phenylhydrazonepropanedinitriles [XC₆H₄NNC(CN)₂]^— (X = H or NO₂) is described. The structures of the following complex compounds are determined by X‐ray diffraction on single crystals: [Ag{O₂NC₆H₄NNC(CN)₂}] ( 2 ), [Ag{C₆H₅NNC(CN)₂}(PPh₃)] · CH₂Cl₂ ( 3 · CH₂Cl₂), [Ag{C₆H₅NNC(CN)₂}(PPh₃)₂] · 0, 5 CH₂Cl₂ ( 4 · 0, 5 CH₂Cl₂) and [Ag(PPh₃)₄][C₆H₅NNC(CN)₂] ( 5 ). In these complexes a variety of coordination modes of the phenylhydrazonepropanedinitrile anions are observed. In 3 and 4 the phenylhydrazonide anion is coordinated via the hydrazone nitrogen atom N(2). 2 shows the structure of a coordination polymer, where the phenylhydrazone coordinates as a tridentate ligand through both nitrile nitrogen atoms and the hydrazone nitrogen atom N(2). In 5 appears a free, non coordinated phenylhydrazonide anion.     

Quecksilber(II)‐chlorid‐ und ‐iodid‐Komplexe von Dithia‐ und Tetrathiakronenethern

Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl₂)₂((ch)₂30S₄O₆)] ( 1 ), [HgCl₂(mn21S₂O₅)] ( 2 ), [HgCl₂(ch18S₂O₄)] ( 3 ) and [HgI(meb12S₂O₂)]₂[Hg₂I₆] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl₂)₂((ch)₂30S₄O₆)] two HgCl₂ units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)₂30S₄O₆) forming a binuclear complex. HgCl₂ forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S₂O₅) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S₂O₄) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S₂O₂) ligand gave with two equivalents HgI₂ the compound [HgI(meb12S₂O₂)]₂[Hg₂I₆]. In the cation [HgI(meb12S₂O₂)]⁺ meb12S₂O₂ forms with the cation HgI⁺ a half‐sandwich complex.     

Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N,N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

Metal Complexes with N₂O₂S₂ Donor Set. Synthesis and Characterization of the Cobalt(II), Nickel(II), and Copper(II) Complexes of a 15‐ and a 16‐Membered Bis(2‐hydroxyethyl) Pendant Macrocyclic Ligand The macrocyclic ligands 6, 10‐bis(2‐hydroxyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecine ( 1 ) (L¹) and 5, 13‐bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecine (L⁴) have been prepared. They form the stable complexes [CoL¹(‐H)CoL¹](ClO₄)₃ ( 2 ), [NiL¹](ClO₄)₂·MeOH ( 3 ), Λ‐[CuL¹](ClO₄)₂·MeOH ( 4a ) and rac‐[CuL¹](ClO₄)₂·MeOH ( 4b ), [NiL⁴](ClO₄)₂ ( 5 ), and [CuL⁴](ClO₄)₂ ( 6 ). The compounds 1 to 6 have been characterized by standard methods and single‐crystal X‐ray diffraction. In the complexes 2 to 6 the metal atoms are octahedrally coordinated by the N₂O₂S₂ donor set of the ligands. L¹ and L⁴ are folded herein along the N···M···S‐ and the N···M···N′‐axes, respectively. This results at the metal atom in a all‐cis‐configuration for the complexes of L¹ and a trans‐N₂‐cis‐O₂‐cis‐S₂‐configuration for the complexes of L⁴. The cobalt(II) complex 2 is a dimer, bridged by a rather short hydrogen bridge of 2.402(12)Å length. The copper(II) complexes of L¹ and L⁴ differ with respect to the Jahn‐Teller‐distortion.     

Phosphaniminato‐Acetato‐Komplexe von Cobalt und Cadmium mit M4N4‐Heterocuban‐Struktur

Phosphoraneiminato‐Acetato Complexes of Cobalt and Cadmium with M₄N₄ Heterocubane Structure The phosphoraneiminato‐acetato complexes [M(NPEt₃)(O₂C–CH₃)]₄ with M = Co and Cd are formed from the anhydrous metal(II) acetates with excess Me₃SiNPEt₃ at 180 °C. By crystallization from diethyl ether blue, moisture sensitive single crystals of [Co(NPEt₃) · (O₂C–CH₃)]₄ can be obtained, while colourless single crystals of [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂ originate from dichloromethane solution. In vacuo the intercalary CH₂Cl₂ is released. The complexes are characterized by their IR spectra and by crystal structure analyses. In both complexes the metal atoms are associated via μ₃–N bridges of the (NPEt₃^–) groups to form heterocubanes. In the cobalt complex the acetato ligands are bonded in a semichelate fashion with a short Co–O and a long Co–O bond each (Co–O distances in average 199.5 and 257.4 pm). In the cadmium complex the acetato groups form almost symmetrical chelates (Cd–O distances in average 232.1 and 237.8 pm); this leads to a distorted trigonal‐bipyramidal arrangement at the cadmium atoms. [Co(NPEt₃)(O₂C–CH₃)]₄: Space group P 1, Z = 4, lattice dimensions at –60 °C: a = 1110.1(2), b = 2051.3(5), c = 2169.5(4) pm, α = 100.03(2)°, β = 103.404(15)°, γ = 97.63(2)°, R = 0.0480. [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂: Space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1550.2(1), b = 2101.1(1), c = 1706.1(1) pm, β = 91.09(1)°, R = 0.0311.     

Heterodinukleare Cobalt(II)‐, Nickel(II)‐, Kupfer(II)‐, Zink(II)und Palladium(II)‐Komplexe mit einem makrocyclischen Liganden vom Schiff‐Basen‐Typ: Synthesen und Strukturen

Complexes with Macrocyclic Ligands. IV. Heterodinuclear Cobalt(II), Nickel(II), Copper(II), Zinc(II) and Palladium(II) Complexes with a Macrocyclic Ligand of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of nickel(II), copper(II), and palladium(II) complexes, [ML^Ph] ( 3 ; L^Ph = N,N′‐phenylene‐bis(3‐formyl‐5‐tert.‐butyl‐salicylaldimine)), are described. These neutral mononuclear complexes react with metal(II) perchlorate and 1,3‐propylenediamine to form heterodinuclear, macrocyclic, cationic complexes of the type [MM′(L^Ph,3)]²⁺ ( 4 ; M = Ni, Cu, Pd; M′ = Co, Cu, Zn). The structures of the five new compounds [NiCo(L^Ph,3)](ClO₄)₂, [NiCu(L^Ph,3)](ClO₄)₂, [CuCu(L^Ph,3)](ClO₄)₂, [CuZn(L^Ph,3)](ClO₄)₂, and [PdCu(L^Ph,3)](ClO₄)₂ were determined by X‐ray diffraction.     

Palladium(II)‐ und Platin(II)‐Komplexe mit dem Antimalariamittel Mefloquin als Liganden

Metal Complexes of Biologically Important Ligands. CXXVI. Palladium(II) and Platinum(II) Complexes with the Antimalarial Drug Mefloquine as Ligand The coordination sites of the antimalarial drug mefloquine (L) were studied. Reactions of the chloro bridged complexes (allyl)Pd(μ‐Cl)₂Pd(allyl) and (R₃P)(Cl)M(μ‐Cl)₂M(Cl)(PR₃) (M = Pd, Pt) with racemic mefloquine give the compounds (allyl)(Cl)Pd(L) ( 1 ), Cl₂(Et₃P)Pt(L) ( 2 ) and Cl₂(Et₃P)Pd(L) ( 3 ) with coordination of the piperidine N atom of mefloquine. In the presence of NaOMe the N,O‐chelate complexes Cl(Et₃P)Pt(L–H⁺) ( 4 ) and Cl(R₃P)Pd(L–H⁺) ( 5 , 6 , R = Et, nBu) were obtained. Protection of the piperidine N atom of mefloquine by protonation allows the synthesis of the complexes Cl₂(Et₃P)Pt(L + H⁺) ( 7 ) in which mefloquine is coordinated via the quinoline N atom. The structures of 2 , 3 and 4 were determined by X‐ray diffraction analysis. In the crystal of 4 pairs of enantiomers are found which are linked by two hydrogen bridges between the amine group and the chloro ligand.     

Synthese und Charakterisierung von Cobalt(II)‐ und Kupfer(I)‐Komplexen mit Guanidin‐Pyridin‐Hybridliganden

Syntheses and Structures of Cobalt(II) and Copper(I) Complexes with Guanidine‐Pyridine Hybridligands The guanidine‐pyridine hybridligands N‐(1,3‐dimethylimidazolidin‐2‐ylidene)‐2‐(pyridine‐2‐yl)ethanamine (DMEGepy, L1 ) and 1,1,3,3‐tetramethyl‐2‐(2‐(pyridine‐2‐yl)ethyl)guanidine (TMGepy, L2 ) have been synthesized and characterized. The reaction of DMEGepy with CoCl₂ and TMGepy with CuI lead to the mononuclear complexes {N‐(1,3‐dimethylimidazolidin‐2‐ylidene)‐2‐(pyridine‐2‐yl)ethanamine}cobalt(II) dichloride ( 1 ) and {1,1,3,3‐tetramethyl‐2‐(2‐(pyridine‐2‐yl)ethyl)guanidine}copper(I) iodide ( 2 ). By the characterization of these complexes we are able to compare the complexation chemistry of the hybridguanidine and bisguanidine ligands with regard to the various N donor functions systematically.     

Synthese und Kristallstruktur von Silber(II)‐Fluoriden AgMIVF6 (MIV = Sn,Ti, Pb,Pd, Pt,Rh)

Synthesis and Crystal Structure of Silver(II) Fluorides AgM^IVF₆ (M^IV = Sn, Ti, Pb, Pd, Pt, Rh) For the first time single crystals of AgSnF₆ (light blue, triclinic with a = 519.93(7) pm, b = 524.96(10) pm, c = 563.13(9) pm, α = 115.66(2)°, β = 89.28(2)°, γ = 118.77(2)°, spcgr. P1–C ; (No. 2), Z = 1) and AgPdF₆ (brown green, triclinic with a = 501.5(2) pm, b = 508.7(2) pm, c = 996.4(2) pm, α = 89.58(2)°, β = 103.10(2)°, γ = 120.88(2)°, spcgr. P1–C , (No. 2), Z = 2) have been synthesized and investigated. Other compounds of this type, like AgTiF₆ and AgPbF₆ (isotypic to AgSnF₆) or AgPtF₆ and AgRhF₆ (isotypic to AgPdF₆) have been synthesized in form of microcrystalline powders, their lattice parameters have been determined by Guinier data. All compounds are structure variants oft the LiSbF₆‐type and isotypic with CuMF₆ (M = Ti, Sn, Pb and Pd, Pt, respectively).     

Synthese und Struktur von Ruthenium(II)‐Komplexen mit Triazenido‐ und Pentaazadienido‐Liganden

Synthesis and Crystal Structure of Ruthenium(II) Complexes with Triazenido and Pentaazadienido Ligands The ruthenium(II) triazenido complex [RuCl(ClC₆H₄N₃C₆H₄Cl)(p‐cymene)] ( 1 ) is obtained by the reaction of silver bis(p‐chlorphenyl)triazenid with [RuCl₂(p‐cymene)]₂ in CH₂Cl₂, and forms air stable, orange yellow crystals. It crystallizes as 1 ·CH₂Cl₂ in the orthorhombic space group Pbca with the lattice parameters a = 3134.3(3), b = 2105.7(2), c = 769.15(4) pm and Z = 8. In the diamagnetic mononuclear complex 1 the chelating triazenido ligand coordinates with the atoms N(1) and N(3). p‐Cymene binds η⁶ with its C₆ ring. The reaction of the etherphosphane complex [RuCl₂(Ph₂PCH₂C₄H₇O₂)₂] with 1, 3‐bis(p‐tolyl)triazenid in THF yields the complex [RuCl(tolyl‐N₃‐tolyl)(Ph₂PCH₂C₄H₇O₂)₂] ( 2 ). 2 forms monoclinic, red crystals with the space group P2₁/c and a = 1521.0(2), b = 1451.8(2), c = 2073.7(2) pm, β = 99.29(1)° and Z = 4. It is air stable and diamagnetic. The triazenide ion coordinates with the atoms N(1) and N(3). One of the two etherphosphane ligands is chelating and coordinates with the P atom and one O atom, while the other ligand binds in a monodentate fashion with its P atom, resulting in a coordination number of six for the Ru^II. [Ag(tolyl‐N₅‐tolyl)]₂ reacts in THF with [RuCl₂(C₆H₆)]₂ to afford the air stable, diamagnetic pentaazadienido complex [RuCl(tolyl‐N₅‐tolyl)(C₆H₆)] ( 3 ). 3 forms monoclinic, red crystals with the space group P2₁/c and a = 1462.4(1), b = 1056.51(8), c = 1371.4(1) pm, β = 114.36(1)° and Z = 4. The chelating pentaazadienido ligand coordinates with the atoms N(1) and N(3) at the divalent Ru atom. The benzene molecule binds η⁶ with its π system.     

N,N-Dimethylglycinatokomplexe von Platin(IV)

N,N -Dimethylglycinato Complexes of Platinum(IV) The aquapentachloroplatinic acid (H₃O)-[PtCl₅(H₂O)] · 2(18-cr-6) · 6 H₂O ( 1 ) reacts with N,N-dimethylglycine (Me₂glyH) to give cis-[PtCl₂(N,O-Me₂gly)₂] · (18-cr-6) ( 6 ) and (Me₂glyH₂)[PtCl₄(N,O-Me₂gly)] ( 7 ). Complexes 6 and 7 are characterized by microanalysis, ¹H-NMR and IR spectroscopy as well as by X-ray structure analysis. In both complexes the N,N-dimethylglycinato ligands are N,O-coordinated. In 6 , the amino groups are mutually trans and the carboxylato groups are cis (configuration index: OC-6–22). In the crystal, there are only weak C–H…O interactions between the N-methyl groups of the [PtCl₂(N,O-Me₂gly)₂] complex and the oxygen atoms of the crown ether (shortest C…O contacts: 3.10(2) Å and 3.21(2) Å). In the solid state, 7 exhibits strong cation-anion interactions: The carboxyl group of the cation (Me₂glyH₂)⁺ forms a strong O–H…O bridge to the exocyclic oxygen atom of the carboxylate group of the glycinato ligand (O…O 2.61(1) Å).     

Tris{2‐[N‐(diethylaminothiocarbonyl)benz(‐amidino;‐imidoxy;‐imidothio)‐N′‐yl]ethyl}amine – neue tripodale Liganden. Darstellung,Komplexstabilität und Extraktionsverhalten ihrer Silber(I)‐Komplexe

Tris{2‐[ N ‐(diethylaminothiocarbonyl)benz(‐amidino; imidoxy; ‐imidothio)‐ N ′‐yl]ethyl}amines – New Tripodal Ligands. Synthesis, Complex Stability, and Extraction Behaviour of their Silver(I) Complexes N‐(Thiocarbamoyl)‐benzimidoylchlorides react with trivalent nucleophiles to give four novel tripodal ligands. Two of them have been characterized by X‐ray methods. The ligands form with silver(I) cationic mononuclear complexes in which the three arms of the ligand are coordinated monodentately via sulfur. The results of FAB and ESI mass spectrometry as well as ESCA and NMR investigations verify this binding mode. The protonation constants of the ligands and the stability constants of silver(I) complexes have been determined potentiometrically. The novel tripodal compounds behave as powerful extractands for silver(I).     

Darstellung und Strukturanalyse neuer Komplexe von Eisen(II), Cobalt(II) und Nickel(II) nach synergistischer Extraktion

Zusammenfassung Die synergistische Extraktion von Eisen(II)-, Cobalt(II)- und Nickel(II)-Komplexen wird untersucht. Verwendet werden fluorierte Diketone (A) (Derivate des Thenoyltrifluoracetons) und eine neue Gruppe Schiff' scher Basen. Aus den Extraktionskurven nach der Job- und Molar-Ratio-Methode, der Elementaranalyse und aus Molmassenbestimmungen werden Komplexverbindungen der Zusammensetzung [M₄A₈B⁴] nachgewiesen. Aus den Elektronen- und IR-Spektren und aus magnetischen Messungen wird für die Ni(II)-Komplexe eine octaedrische Struktur vorgeschlagen.

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Preparation and structure analysis of new iron(II), cobalt(II) and nickel(II) complexes by synergistic extraction

Summary The synergistic extraction of iron(II), cobalt(II) and nickel(II) complexes was investigated. Fluorinated diketones (A) (derivates of thenoyltrifluoracetones) and a new group of Schiff bases were used. By Job and molar-ratio method investigation on the extraction curves, by elementary analysis and molar mass detection, complex compounds of the composition [M₄A₈B⁴] could be proved. Electron and infrared spectra and magnetical measurements led to an octahedral structure proposal for the Ni(II)-complexes.

Mein Dank gilt besonders Herrn Professor Dr. H. Specker, Direktor des Instituts für Anorganische Chemie I der RUB, für die Zurverfügungstellung der Geräte und Chemikalien, Herrn Professor Dr. Metfessel und Frau Dr. Magdela Gronau für die magnetischen Messungen in der Abteilung Physik der RUB.     

Syntheses,Characterization and X‐Ray Structures of the first Copper(I) and Silver(I) Complexes with ATT (ATT = 6‐Aza‐2‐thiothymine)

The reaction of copper(I) chloride with 6‐aza‐2‐thiothymine (ATT, 1 ) and triphenylphosphane in methanol/chloroform gives [(ATT)CuCl(PPh₃)] ( 2 ) as a neutral complex. [(ATT)Ag(NO₃)(PPh₃)₂]·MeOH ( 3 ) can be obtained by the reaction of 1 with silver(I) nitrate and triphenylphosphane in methanol/chloroform in excellent yields and the single crystals of 3 can be obtained from acetonitril solution. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at —80 °C: space group I2/a with a = 1859.3(1), b = 1143.2(1), c = 2208.2(1) pm, β = 104.84(1)°, Z = 8, R₁ = 0.0355 and for 3 at —80 °C: space group P2₁/c with a = 1344.1(1), b = 1553.6(1), c = 1977, 3(3) pm, β = 105.26(1)°, Z = 4, R₁ = 0.0436.     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Das SCN–-Ion als ambidenter Ligand – Synthese und Kristallstrukturen von (Bu4N)4[Ag2Fe2(SCN)12] und (Et4N)2 [Ag2Fe(SCN)6]

The SCN^– Ion as an Ambidentate Ligand – Synthesis and Crystal Structures of (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] and (Et₄N)₂ [Ag₂Fe(SCN)₆] In (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] · 2 CH₃NO₂ ( 1 ) and (Et₄N)₂[Ag₂Fe(SCN)₆] ( 2 ) the ambidentate SCN^– anions link Ag⁺ with Fe³⁺ and Fe²⁺ centers, respectively. The tetranuclear anions in 1 are built from [Fe(NCS)₆]^3– groups connected by Ag⁺ ions. In 2 the same bridging pattern leads to polymeric anionic chains containing [Fe(NCS)₆]^4– groups linked by Ag⁺ ions. (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] · 2 CH₃NO₂ ( 1 ): a = 1184.10(10), b = 1370.80(10), c = 1776.5(2) pm, α = 99.090(10), β = 102.100(10), γ = 100.360(10)°, V = 2715.5(4) · 10⁶ pm³, space group P1; (Et₄N)₂[Ag₂Fe(SCN)₆] ( 2 ): a = 1607.0(2), b = 1006.92(9), c = 1096.13(9) pm, V = 1773.7(3) · 10⁶ pm³, space group Pnnm.     

Molybdän‐ und Wolfram‐Komplexe mit MNS‐Sequenzen. Die Kristallstrukturen von [MoCl3(N3S2)(1,4‐Dioxan)2] und [Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2

Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of [MoCl₃(N₃S₂)(1,4‐dioxane)₂] and [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ The cyclo‐thiazeno complexes [Cl₃MNSNSN]₂ of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes [μ‐(1,4‐dioxane){MCl₃(N₃S₂)}₂] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex [MoCl₃(N₃S₂)(1,4‐dioxane)₂] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN^2–) complex [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ has been obtained by the reaction of [MoN(OCMe₃)₃] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo₂N₂ fourmembered ring. [MoCl₃(N₃S₂)(1,4‐dioxane)₂]: Space group P2₁/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R₁ = 0.0317. [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ · 4 CCl₄: Space group P2₁/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R₁ = 0.0507.     

Pyridin‐Komplexe von Seltenerd‐Trichloriden. Synthese und Kristallstrukturen von [YCl3(Py)4] und [LnCl3(Py)4] · 0,5 Py mit Ln = La und Er

Pyridine Complexes of Rare Earth Element Trichlorides. Syntheses and Crystal Structures of [YCl₃(py)₄] and [LnCl₃(py)₄] · 0.5 py with Ln = La and Er The pyridine complexes [YCl₃(py)₄] ( 1 ), [LaCl₃(py)₄] · 0.5 py ( 2 · 0.5 py), and [ErCl₃(py)₄] · 0.5 py ( 3 · 0.5 py) have been prepared from the diacetone‐alcohol complexes [LnCl₃(DAA)₂] or directly from the metal trichlorides with excess pyridine to give colourless, only sparingly moisture sensitive crystals. They were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group Pbca, Z = 16, lattice dimensions at –80 °C: a = 1647.4(1), b = 1743.1(1), c = 3190.5(1) pm, R₁ = 0.031. 2 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 978.9(1), b = 1704.5(1), c = 1589.5(1) pm, β = 103.61(1)°, R₁ = 0.0281. 3 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 970.1(1), b = 1706.4(1), c = 1566.1(1) pm, β = 103.46(1)°, R₁ = 0.0232. All complexes realize monomeric molecular structures with the metal atom in a distorted pentagonal‐bipyramidal coordination. One of the chlorine atoms and the four pyridine molecules are in the equatorial plane.     

Diacetonalkohol‐Komplexe von Lanthanoid‐Trichloriden. Die Kristallstrukturen von [LnCl3(DAA)2] mit Ln = Sm und Eu

Diacetone Alcohol Complexes of Lanthanide Trichlorides. Crystal Structures of [LnCl₃(DAA)₂] with Ln = Sm and Eu The diacetone alcohol complexes [LnCl₃(DAA)₂] with Ln = samarium ( 1 ) and europium ( 2 ) are obtained from the waterfree metal trichlorides with excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanone = DAA) forming colourless ( 1 ) and pale yellow crystals ( 2 ), respectively, which are characterized by crystal structure determinations. The europium compound 2 is additionally described by its vibrational spectra (IR, Raman). 1 and 2 crystallize isotypically with one another. The metal atoms of the molecular complex units are unusually coordinated in a distorted pentagonal‐bipyramdial fashion by the three chlorine atoms and by the two alcoholic oxygen atoms of the DAA molecules in the equatorial plane. The apical positions are occupied by the carbonyl oxygen atoms of the chelating DAA molecules. The complex units [LnCl₃(DAA)₂] are associated along [100] by bifurcated —OH···Cl···HO— bridges to form chains. 1 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: : a = 710.2(1), b = 1617.6(2), c = 827.3(1) pm; β = 106.36(1)°; R₁ = 0.026. 2 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: a = 709.7(1), b = 1614.5(2), c = 825.7(1) pm; β = 106.40(1)°; R₁ = 0.0303.