Titanocen-cyandithioformiat-Komplexe

The reaction of titanocene dichloride,Cp ₂TiCl₂ (Cp=⁵-C₅H₅), with one or two equivalents of sodium cyanodithioformate affords the new mono- or bis(dithiocarboxylato) derivativesCp ₂TiCl(S₂CCN) (1) andCp ₂Ti(S₂CCN)₂ (2). Elimination of sulfur converts2 into the metallacyclicCp ₂TiS₂C₂(CN)₂ (3), which does not react with the diene isoprene, but can be reconverted into the appropriate titanocene dihalides by chlorine or bromine.

     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

Separation of dihydrogenpolysulphides (polysulphanes) using reversed-phase HPLC

Summary The reaction of Na₂S _n (from Na₂S + S₈) with SCl₂ in anhydrous and deaerated alcohols (C₁ to C₅) yields polysulphanes, H₂S _n , which were identified by HPLC at a bonded C₁₈ phase with methanol eluent, as well as by some typical reactions. Chain lengths up to n=16 were found. The H₂S _n decompose slowly under Ar, yielding H₂S and sulphur homocycles S _n–1. With alkali they are rapidly decomposed to H₂S and S₈. The retention of H₂S _n is much closer to that of the sulphur ring having the same sulphur atom number than to that of dialkylpolysulphide of comparable molecular size. The SH-groups cause only very little increase in solute solvophilic properties.

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Trennung von Dihydrogenpolysulfiden (Polysulfanen) durch Reversed-Phase-HPLC

Zusammenfassung Bei der Reaktion von Na₂S _n (aus Na₂S + S₈) in Alkoholen (C₁ bis C₅) mit SCl₂ unter Argon entstehen Produkte, die aufgrund ihres Verhaltens bei der HPLC an einer C₁₈-Phase mit rein methanolischem Eluens sowie durch einige Reaktionen als Polysulfane H₂S _n erkannt wurden. S-Ketten bis n=16 wurden gefunden. Die H₂S _n zersetzen sich unter Ar langsam zu H₂S und Schwefelringen H₂S _n–1. Durch Alkali zerfallen sie sehr schnell in H₂S und S₈. Die Retention der H₂S _n ist der der Schwefelringe mit gleichem n viel ähnlicher als der etwa gleich großer Dialkylpolysulfide. Die SH-Gruppen haben nur einen sehr kleinen solvophilen Effekt.

     

Rh(III), Pd(II), Pt(IV) and Au(III) complexes of 2-thiopyrimidine derivatives

Some news thiopyrimidine derivatives and complexes [4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidine (TANH), its 2-methylthio derivative (MTH), the ammonium salt ofTANH (sTANH) and six new complexes of formulas: Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃ Pd(TANH)₂Cl₂ and Au(TAN ^–)Cl] have been synthesized and characterized by elemental analysis, IR and¹H-NMR spectroscopy techniques. The thermal behaviour of all compounds has also been studied.

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Rh(III), Pd(II), Pt(IV) und Au(III) Komplexe von 2-Thiopyrimidin Derivaten

Zusammenfassung Es wurden einige neue Thiopyrimidinderivate und deren Komplexe synthetisiert und mittels Elementaranalyse, IR und¹H-NMR charakterisiert: 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidin (TANH), dessen 2-Methylthio-Derivat (MTH), das Ammoniumsalz vonTANH (sTANH) und sechs neue Komplexe der Formeln Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃, Pd(TANH)₂Cl₂ und Au(TAN ^–)Cl. Das thermische Verhalten der Verbindungen wurde ebenfalls untersucht.

     

Cp2Ti{[OC(O)C5H4]Cr(CO)2NO]}2 and Cp2Ti{[(OC(O)C5H4]Cr(NO)2X}2 syntheses and spectra of chromium-titanium complexes bridged by carboxylate substituted cyclopentadienyl group

Complete demethylation of Cp₂Ti(CH₃)₂ in dichloromethane with 2 M equivalent of [η⁵-(C₅H₄COOH)]Cr(CO)₂NO (5), [η⁵-(C₅H₄COOH)]Cr(NO)₂X] (X = Cl 6, X = I 7), and [η⁵-(C₅H₄COOH)]W(CO)₃CH₃ (8); gives Cp₂Ti{[OC(O)C₅H₄]Cr(CO)₂NO}₂ (13), Cp₂Ti{[OC(O)C₅H₄]Cr(NO)₂Cl}₂ (14), Cp₂Ti{[OC(O)C₅H₄]Cr(NO)₂I}₂ (15),and Cp₂Ti{[OC(O)C₅H₄]W(CO)₃CH₃}₂ (16), respectively. The chemical shifts of C(2)-C(5) carbon atoms of compounds 13-15 have been assigned using two-dimensional HetCOR NMR spectroscopy. The assigned chemical shifts were compared with the NMR data of their analogues of ferrocene, and the opposite correlation on the assignments was observed for cynichrodenoyl moieties.     

Syntheses and spectra of chromium-titanium complexes bridged by carboxylate substituted cyclopentadienyl group: The structure of Cp2Ti(CH3){[OC(O)C5H4]Cr(NO)2Cl}

Mono-demethylation of Cp₂Ti(CH₃)₂ in dichloromethane with 1 M equivalent of [η⁵-(C₅H₄COOH)]Cr(CO)₂NO (5), [η⁵-(C₅H₄COOH)]Cr(NO)₂X] (X = Cl 6, X = I 7) and [η⁵-(C₅H₄COOH)]W(CO)₃CH₃ (8) gives Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(CO)₂NO} (9), Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(NO)₂Cl} (10), Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(NO)₂I} (11) and Cp₂Ti(CH₃){[OC(O)C₅H₄]W(CO)₃CH₃} (12), respectively. The structure of 10 has been solved by X-ray diffraction studies. One of the nitrosyl groups is located at the site away from the exocyclic carbonyl carbon of the Cp(Cr) ring with twist angle of 178.1°. All the data reveals that Cp₂Ti(CH₃)- is a strong electron-donating group. The opposite correlation was observed on the chemical shift assignments of C(2)-C(5) in compounds 5-12, using HetCOR NMR spectroscopy, as compared with the NMR data of their ferrocene analogues. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of ¹³C NMR data and those of 10 are compared with the calculations via density functional B3LYP correlation- exchange method.     

Thiochloroarsenate(III): Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SCl5] und (PPh4)2[As2SCl6] · C2H4Cl2

Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh₄[As₂SCl₅] and (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂ PPh₄[As₂SCl₅] can be obtained from As₂S₃ + PPh₄Cl with HCl in CH₂Cl₂ or 1,2-C₂H₄Cl₂. It reacts with a second mole of PPh₄Cl to yield (PPh₄)₂[As₂SCl₆]. The latter also is formed by the reaction of As₂S₅ + 2 PPh₄Cl with HCl, a second product being (PPh₄)₂[As₂Cl₈]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh₄[As₂SCl₅], monoclinic, space group P2₁/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As₂SCl₅]⁻ ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As₂SCl₆]²⁻ ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom.     

Titanium complexes with sulfur‐linked bis(phenolate) ligands

High‐quality crystals of two bis(phenolate)titanium complexes, namely dichlorido{4,4′‐dimethyl‐2,2′‐[cyclohexane‐1,2‐diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C₂₀H₂₂O₂S₂)Cl₂], (I), and dichlorido{2,2′‐[cyclohexane‐1,2‐diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C₁₈H₁₈O₂S₂)Cl₂], (II), were obtained by reactive crystallization. Depending on the solvent, compound (II) was obtained as unsolvated (IIa) or as the toluene hemisolvate, [Ti(C₁₈H₁₈O₂S₂)Cl₂]·0.5C₇H₈, (IIb). These systems without bulky substituents on the aromatic phenolate rings serve as ideal model compounds for precatalysts. The excellent X‐ray diffraction data will help clarify the nature of the mismatched interactions between the soft S atoms within the ligand and the hard titanium center. Molecule (I) has crystallographic C₂ symmetry.     

Synthesis and physico-chemical studies of some polynuclear mixed carboxylate complexes of nickel(II)

A number of polynuclear mixed carboxylates of nickel(II) with the general composition [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (whereR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ and C₂₁H₄₃ andn=1 or 2) have been synthesized by the transacylation reactions of anhydrous nickel acetate with higher carboxylic acids in refluxing toluene. On recrystallization from benzene-alcohol mixtures, mono-alcoholate complexes, Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (whereR=CH₃ and C₂H₅) have been isolated. All these derivatives have been characterized by the molecular weight determinations, infra-red and electronic reflectance spectra and magnetic susceptibility measurements.

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Synthese und Eigenschaften einiger gemischter Carboxylat-Komplexe von Nickel(II)

Zusammenfassung Komplexe des Typs [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (mitR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ und C₂₁H₄₃,n=1 oder 2) wurden aus wasserfreiem Nickelacetat mit höheren Carbonsäuren in siedendem Toluol erhalten. Bei der Kristallisation aus Benzol-Alkohol-Mischungen wurden Monoalkoholate Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (mitR=CH₃ und C₂H₅) isoliert. Die Charakterisierung der Komplexe erfolgte mittels Molekulargewichtsbestimmung, Infrarot- und Elektronenspektren und der Messung der magnetischen Susceptibilität.

     

Metal complexes of the diuretic drug furosemide

New complexes of the formulaeM(fur)₂·2H₂O (M = Mn, Cu, Zn),M(fur)₂·3H₂O (M = Co, Ni, Cd), Hg₂(fur)₃Cl₂·2H₂O, Pd(fur)Cl·H₂O and Rh(fur)₃·3H₂O, wherefurH = 4-chloro-N-(2-furfuryl)-5-sulfamoylanthranilic acid, have been prepared and characterized by conductivity measurements, X-ray powder patterns, thermal methods, effective magnetic moments as well as by IR, ligand field,¹H-NMR and ESR spectroscopic studies. The anionfur ^– shows a chelated bidentate O(carboxylato), N(imino)-coordinating behaviour.

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Metallkomplexe der diuretischen Droge Furosemid

Zusammenfassung Neue Komplexe der Verbindungen:M(fur)₂·2H₂O (M = Mn, Cu, Zn),M(fur)₂·3H₂O (M = Co, Ni, Cd), Hg₂(fur)₃Cl₂·2H₂O, Pd(fur)Cl·H₂O und Rh(fur)₃·3H₂O, wobeifurH 4-chlor-N-(2-furfuryl)-5-sulfamoylanthanilsäure ist, wurden dargestellt. Die Komplexe wurden durch Leitfähigkeitsmessungen, Röntgen-Pulver-Aufnahmen, thermogravimetrische Analysen, Messungen des effektiven magnetischen Dipolemomentes sowie durch spektroskopische Untersuchungen (IR,¹H-NMR und ESR) charakterisiert. Das Anionfur ^– zeigt das Verhalten einer Chelat-bidentat-O(carboxylato),N(imino)-Koordination.

     

S-(N-(Thiocarbamoyl)benzimido)-dithiocarbamidsäureester

Zusammenfassung Die Synthese der Titelverbindungen3 (R ¹=R ²=C₂H₅;n-C₄H₉) durch Reaktionen von N-(N,N-Diethylthiocarbamoyl)-benzimidoylchlorid (2) mit Natriumdialkyldithiocarbamaten (1) in Aceton wird beschrieben. Die niedrigen Ausbeuten (bis 25% d.Th.) sind durch Nebenreaktionen bedingt. Die Strukturen der Verbindungen werden durch IR-,¹H-NMR-,¹³C-NMR-und Massenspektren bestätigt. Nebenreaktionen werden¹³C-NMR-spektroskopisch verfolgt und die Ergebnisse diskutiert.

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S-(N-(thiocarbamoyl)benzimido)dithiocarbamic esters

Summary The synthesis of the title compounds3 (R ¹=R ²=C₂H₅;n-C₄H₉) by reactions of N-(N,N-diethylthiocarbamoyl)benzimidechloride (2) with sodiumdialkyldithiocarbamates (1) in acetone is described. The low yields (<25%) are caused by the occurrence of side reactions. The structures of the compounds were confirmed by IR,¹H and¹³C NMR, and mass spectroscopy. Side reactions were detected by¹³C NMR spectroscopy; the results are discussed.

     

Compounds of oxozirconium(IV) alkoxides with oxygen and nitrogen bases

Pyridine, quinoline, 2,2-bipyridyl, dimethylformamide, dimethylacetamide and phthalimide combine with ZrOCl(OCHMe ₂)·2Me ₂CHOH to form complexes, ZrOCl(OCHMe ₂)·Base [with the exception of dimethylsulfoxide: Zr₂O₂Cl₂(OCHMe ₂)₂·3DMSO], whereas dialkoxides, ZrO(OR)₂·ROH (R=Me, Et, Pr ⁱ ), fail to react. The complexes have been characterized through infrared, molar conductance and thermal decomposition studies.

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Komplexe von Oxozirkonium(IV)-Alkoxiden mit Sauerstoff- und Stickstoff-Basen

Zusammenfassung Pyridin, Chinolin, 2,2-Bipyridyl, Dimethylformamid, Dimethylacetamid und Phthalimid geben mit ZrOCl(OCHMe ₂)·2Me ₂CHOH Komplexe vom Typ ZrOCl(OCHMe ₂)·Base [ausgenommenDMSO: Zr₂O₂Cl₂(OCHMe ₂)₂·3DMSO], während Dialkoxide, ZrO(OR)₂·ROH (R=Me, Et, Isopr), keine Reaktion ergeben. Die Komplexe wurden durch ihre IR-Spektren, molare Leitfähigkeit und mittels Untersuchung der thermischen Zersetzung charakterisiert.

     

New Titanocene Complexes [Cp2Ti(μ-S2)2NR] (with R = Me and n Oct) as Transfer Reagents for the Synthesis of the Heterocycles S5NR and S6NR

The reaction of 1,4-S₄(NR)₂ with (η⁵-C₅H₅)₂Ti(CO)₂ yields [C_p2Ti(μ-S₂)₂NR] which on treatment with SCl₂ or S₂Cl₂ provides the novel heterocycles S₅NR and S₆NR (R = Me, Oct).     

An Au(III) complex of glycyl- S -serine: a linear polarized IR and 1H- and 13C-NMR investigation

The structure of a mononuclear Au(III) complex of the dipeptide glycyl-S-serine (Gly-Ser) has been predicted using solid-state linear dichroic IR (IR-LD) spectroscopy, based on an orientation technique in a nematic liquid crystal suspension. Results are compared with data from ¹H- and ¹³C-NMR, MS, elemental analysis, thermogravimetry and differential scanning calorimetry. The metal ion is coordinated as a tridentate through NH₂, N (from deprotonated amide) and O (COO^?) groups to form [Au(C₅H₉N₂O₄)Cl], with the fourth position of the square-planar coordination sphere being completed by a Cl^? ion.     

The substitution chemistry of RuCp* (temeda)Cl

Summary Halide abstraction from RuCp*(tmeda)Cl (1,tmeda=Me₂NCH₂CH₂NMe₂) with NaBPh₄ in CH₂Cl₂ leads to the formation of the sandwich complex RuCp*(⁶-C₆H₅BPh₃) (2). In the presence of CH₃CN (1 equiv.) and CO, however, the cationic complexes [RuCp*(tmeda)(CH₃CN)]⁺ (3) and [RuCp*(temeda)(CO)]⁺ (5) are obtained. In CH₃CN,tmeda is also replaced giving [RuCp*(CH₃CN)₃]⁺ (4). Complex1 reacts readily with terminal acetylenes HCCR, the products depending on the nature ofR (Ph, SiMe₃,n-Bu, COOEt). Thus, withR=Ph the ruthenacyclopentatriene complex RuCp*(,-C₄Ph₂H₂)Cl (6), withR=SiMe₃ the cyclobutadiene complex Ru(Cp*)(⁴-C₄H₂(1,2-SiMe₃)₂)Cl (7), and withR=n-Bu and COOEt the binuclear complexes (Cp*)RuCl₂(²:⁴-₂-C₄H₂(1,3-R)₂)Ru(Cp*) (8,9) are obtained. Furthermore, with diethyl maleate in the presence of 1 equiv. of LiCl,1 transforms into the new anionic complex Li[Ru(Cp*) (²-C₂H₂(COOEt)₂)Cl₂] (10). X-ray structures of2,3,4,7, and10 are included.

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Substitutionsreaktionen von RuCp*(tmeda)Cl

Zusammenfassung Chloridabspaltung von RuCp*(tmeda)Cl (1,tmeda=Me₂NCH₂CH₂NMe₂) mittels NaBPh₄ in CH₂Cl₂ führt zur Bildung des Halbsandwich-Komplexes RuCp*(⁶-C₆H₅BPh₃) (2), während in Gegenwart von CH₃CN oder CO die beiden kationischen Verbindungen [RuCp*(tmeda)(CH₃CN)]⁺ (3) und [RuCp*(tmeda)(CO)]⁺ (5) entstehen. In CH₃CN als Lösungsmittel wird sogartmeda unter Bildung von [RuCp*(CH₃CN)₃]⁺ (4) verdrängt. Komplex1 reagiert sehr leicht mit terminalen Alkinen HCCR, wobei die Produkte stark von der Natur des SubstituentenR (Ph, SiMe₃,n-Bu, COOEt) abhängen. Im Fall vonR=Ph entsteht der Ruthenacyclopentatrien-Komplex RuCp*(-C₄Ph₂H₂)Cl (6), mitR=SiMe₃ der Cyclobutadien-Komplex Ru(Cp*)(⁴-C₄H₂(1,2-SiMe₃)₂)Cl (7), und im Fall vonR=n-Bu und COOEt bilden sich die binuklearen Komplexe (Cp*)RuCl₂(²:⁴-₂-C₄H₂(1,3-R)₂)Ru(Cp*) (8,9). Überdies reagiert1 mit Maleinsäurediethylester in Gegenwart von LiCl zum neuen anionischen Komplex Li[Ru(Cp*) (²-C₂H₂(COOEt)₂)Cl₂] (10). Von2,3,4,7 und10 wurden die Kristallstrukturen bestimmt.

     

Transition metal chemistry of oxime-containing ligands,IX

The vibrational (conventional and far-infrared) and diffuse-reflectance spectra in conjunction with magnetic susceptibility measurements over a temperature range down to liquid nitrogen temperature are reported and discussed for the complexes; [Mn(HPOX)₂ X ₂]; [Mn(HMPX)₂ X ₂]; [Fe(HPOX)(POX) X ₂] and [Fe(HMPX)(MPX) X ₂](whereHPOX=pyridine-2-aldoxime (C₆H₆N₂O);POX=C₆H₅N₂O;HMPX=6-Methylpyridine-2-aldoxime (C₇H₈N₂O);MPX=C₇H₇N₂O;X=Cl, Br, I, NO₃, NCS, or OA c andX ₂=SO₄). On the basis of these physical studies a six-coordinated structure is suggested for the manganese(II) and iron(III) complexes.Mössbauer spectra, measured at room-temperature and liquid nitrogen temperature also indicated a six-coordinate geometry for iron(III) complexes.

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Übergangsmetallkomplexe mit Oxim-enthaltenden Liganden, IX. Spektroskopische und magnetische Untersuchungen von Mn(II)- und Fe(II)-Komplexen mit Pyridin-2-aldoxim und 6-Methylpyridin-2-aldoxim

Zusammenfassung Es wurden Komplexe von Pyridin-2-aldoxim (HPOX) und 6-Methylpyridin-2-aldoxim (HMPX) vom Typ [Mn(HPOX)₂ X ₂], [Mn(HMPX)₂ X ₂], [Fe(HPOX)(POX)X ₂] und [Fe(HMPX)(MPX)X ₂] (X=Cl, Br, I, NO₃, NCS, OA c;X ₂=SO₄) dargestellt. Die Diskussion erfolgt basierend auf Infrarot-spektroskopie (inklusive fernes IR), Messungen der magnetischen Suszeptibilität (Temp. bis zu fl. N₂) undMössbauer-Spektroskopie.

     

Succinic,fumaric, adipic and oxalic acid cocrystals of promethazine hydrochloride

Novel cocrystals of promethazine hydrochloride [PTZ‐Cl; systematic name: N,N‐dimethyl‐1‐(10H‐phenothiazin‐10‐yl)propan‐2‐aminium chloride] with succinic acid (PTZ‐Cl‐succinic, C₁₇H₂₁N₂S⁺·Cl^?·0.5C₄H₆O₄), fumaric acid (PTZ‐Cl‐fumaric, C₁₇H₂₁N₂S⁺·Cl^?·0.5C₄H₄O₄) and adipic acid (PTZ‐Cl‐adipic, C₁₇H₂₁N₂S⁺·Cl^?·0.5C₆H₁₀O₄) were prepared by solvent drop grinding and slow evaporation from acetonitrile solution, along with two oxalic acid cocrystals which were prepared in tetrahydrofuran (the oxalic acid hemisolvate, PTZ‐Cl‐oxalic, C₁₇H₂₁N₂S⁺·Cl^?·0.5C₂H₂O₄) and nitromethane (the hydrogen oxalate salt, PTZ‐oxalic, C₁₇H₂₁N₂S⁺·C₂HO₄^?). The crystal structures obtained by crystallization from tetrahydrofuran and acetonitrile include the Cl^? ion in the lattice structures, while the Cl^? ion is missing from the crystal structure obtained by crystallization from nitromethane (PTZ‐oxalic). In order to explain the formation of the two types of supramolecular configurations with oxalic acid, the intermolecular interaction energies were calculated in the presence of the two solvents and the equilibrium configurations were determined using density functional theory (DFT). The cocrystals were studied by X‐ray diffraction, IR spectroscopy and differential scanning calorimetry. Additionally, a stability test under special conditions and water solubility were also investigated. PTZ‐Cl‐succinic, PTZ‐Cl‐fumaric and PTZ‐Cl‐adipic crystallized having similar lattice parameter values, and showed a 2:1 PTZ‐Cl to dicarboxylic acid stoichiometry. PTZ‐Cl‐oxalic crystallized in a 2:1 stoichiometric ratio, while the structure lacking the Cl atom belongs has a 1:1 stoichiometry. All the obtained crystals exhibit hydrogen bonds of the type PTZ…Cl…(dicarboxylic acid)…Cl…PTZ, except for PTZ‐oxalic, which forms bifurcated bonds between the hydrogen oxalate and promethazinium ions, along with an infinite hydrogen‐bonded chain between the hydrogen oxalate anions.     

A new P,S‐coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with PdII and PtII

In our ongoing development of ferrocene ligands, 1‐dimethylamino‐2‐(diphenylphosphinothioyl)ferrocene is being used as a convenient building block to obtain racemic or enantiomerically pure ligands. Using this building block in large excess allowed the formation of several by‐products, two of which have already been reported; the structure of a third by‐product, namely 1‐(diphenylphosphinothioyl)‐2‐{[(diphenylphosphinothioyl)sulfanyl]methyl}ferrocene, [Fe(C₅H₅)(C₃₀H₂₅P₂S₃)], is presented here. The crystal structure is built up from a ferrocene unit, with one of the cyclopentadienyl (Cp) rings substituted in the 1‐ and 2‐positions by a protected diphenylphosphinothioyl group and a [(diphenylphosphinothioyl)sulfanyl]methyl fragment, –CH₂SP(=S)Ph₂. There are C—H...S interactions which result in the formation of chains parallel to the c axis. After desulfurization, the crude material was then reacted with Pd and Pt (M) precursors [MCl₂(CH₃CN)₂] to yield two isostructural dinuclear complexes arranged around twofold axes, namely (R,R/S,S)‐bis{μ‐[2‐(diphenylphosphanyl)ferrocen‐1‐yl]methanethiolato‐κ³P,S:S}bis[chloridopalladium(II)] pentane disolvate, [Pd₂{Fe(C₅H₅)(C₁₈H₁₅PS)}₂Cl₂]·2C₅H₁₂, and the platinum(II) analogue, (R,R/S,S)‐bis{μ‐[2‐(diphenylphosphanyl)ferrocen‐1‐yl]methanethiolato‐κ³P,S:S}bis[chloridoplatinum(II)] toluene monosolvate, [Pt₂{Fe(C₅H₅)(C₁₈H₁₅PS)}₂Cl₂]·C₇H₈, in which the two metal atoms present a slightly distorted square‐planar geometry formed by two bridging S atoms and P and Cl atoms. The P,S‐chelating ligand results from the rupture of one of the P—S bonds in the starting ligand. These dinuclear complexes display a butterfly geometry. Surprisingly, only the (R,R/S,S) diastereoisomer has been isolated.     

Optimized synthesis of selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives

Abstract

Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives were synthesized via substitution reactions through tailored control. The reactions of cyclotriphosphazene with 4-oxybenzaldehyde and 2,2-dioxybiphenyl gave the following synthesized derivatives: one mono-substituted open-chain compound, N₃P₃Cl₅(O₂C₇H₅) (1, 69%); mono spiro, N₃P₃Cl₄(O₂C1₂H₈) (2, 91.1%); non-gem tri-substituted, N₃P₃Cl₃ (O₆C₂₁H₁₅) (3, 17%); dispiro, N₃P₃Cl₂(O₄C₂₄H₁₆) (4, 92.3%); penta-substituted, N₃P₃Cl(O₁₀C₃₅H₂₅) (5, 92%);hexa-substituted, N₃P₃(O₁₂C₄₂H₃₀). Most of these derivatives (1–6) are obtained with good yield (up to 97%), This work provides a simple and available approach to obtain versatile cyclotriphosphazene derivatives, which is expected to further promote the use of HCCP as phosphorus platform for the construction of multi-functional materials.     

New [Ti(η5-C5H5)Cl2(OR)] complexes. Crystal and molecular structure of η5-Cyclopentadienyl(cyclohexoxy)titanium(IV) dichloride

Summary A series of new compounds with molecular formula [Ti(⁵-C₅H₅)Cl₂(OR)] (R=C₆H₁₁ (cyclohexyl,1), CH₂CH(CH₃)₂ (2), CH(C₂H₅)₂ (3), and CH₂C₆H₅ (4)) has been obtained by the reaction of [Ti(⁵-C₅H₅)Cl₃] with the appropriate alcohol. All complexes were characterized by elemental analysis and by IR and¹H NMR spectroscopy. The structure of1 was determined by X-ray diffraction studies; crystal data: triclinic,a=11.334(2),b=13.590(2),c=12.237(2) Å, =113.501(5), =118.182(5), =101.993(6),V=1328.2(4) ų,T=298K, space P1,Z=4, two crystallographically independent molecules in the unit cell. FinalR andR _w values are 0.0583 and 0.0632, respectively. Compound1 exhibits surprisingly short Ti-Cl and Ti-O distances, suggesting strong donation by the chloride and in particular by the alkoxide ligand. The Ti-O-C angle is unusually large.

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Neue [Ti(⁵-C₅H₅)Cl₂(OR)]-Komplexe. Kristall- und Molekülstruktur von ⁵-Cyclopentadienyl(cyclohexoxy)titan(IV) Dichlorid

Zusammenfassung Durch Umsetzung von [Ti(⁵-C₅H₅)Cl₃] mit dem geeigneten Alkohol wurde eine Reihe von neuen Verbindungen der Formel [Ti(⁵-C₅H₅)(OR)] (R=C₆H₁₁ (cyclohexyl,1), CH₂CH(CH₃)₂ (2), CH(C₂H₅)₂ (3) und CH₂C₆H₅ (4)) erhalten. Alle Komplexe wurden elementaranalytisch sowie IR- und¹H-NMR-spektroskopisch charakterisiert. Die Struktur von1 wurde röntgenographisch bestimmt; Kristalldaten: triklin,a=11.334(2),b=13.590(2),c=12.237(2) Å, =113.501(5), =118.182(5), =101.993(6),V=1328.2(4) ų,T=298K, Raumgruppe P1,Z=4, zwei kristallographisch unabhängige Moleküle in der Elementarzelle; abschließendeR-Werte:R=0.0583 undR _w=0.0632. Verbindung1 zeigt überraschend kurze Ti-Cl- und Ti-O-Abstände; dies deutet auf eine starke -Elektronendonorwirkung des Chlorid- und vor allem des Alkoxidliganden hin. Der Ti-O-C-Bindungswinkel ist ungewöhnlich groß.