Kupfer(II)-Komplexe mit para- und diamagnetischen Semicarbazonliganden

A series of complexes formed between the copper(II) metal ion and the semicarbazone of the stable free radical 2-acetyl-2,5,5-trimethyl-4-phenyl-3-imidazoline-3-oxid-1-oxyl and the analogous hydroxylamine has been prepared. By analysis of the IR spectra of the complexes the coordination mode of the ligands was determined.

     

Darstellung und Struktur von Tetraethylcyclotetraarsoxan-Komplexen von Kupfer(I)-Halogeniden

Preparation and Structure of Tetraethylcyclotetraarsoxane Complexes of Copper(I) Halides The polymeric complexes [Cu₄Cl₄{cyclo-(C₂H₅AsO)₄}₃]_n ( 1 ), [Cu₃Br₃{cyclo-(C₂H₅AsO)₄}₂]_n ( 2 ) and [Cu₆I₆{cyclo-(C₂H₅AsO)₄}₃]_n ( 3 ) were prepared by the reaction of (C₂H₅AsO)_n and CuX (X = Cl, Br, I) in acetonitrile and characterised by X-ray analysis. All three complexes contain only tetramers (C₂H₅AsO)₄ as ligands, in which the As₄O₄ ring systems coordinate between two and four Cu-atoms. In each case one As₄O₄ ring with a crown-shaped conformation is observed, which coordinates either four (in 1 ) or three (in 2 and 3 ) axially sited Cu-atoms. In addition there are further (C₂H₅AsO)₄ ligands, which display either a boat-chair- (in 1 ) or a twist-chair-conformation (in 1–3 ). The individual building units are connected to one another via Cu? X? Cu bridges (in 2 and 3 ) and/or centrosymmetric As₄O₄ ring systems (in 1–3 ) into chain ( 1 ) or layer structures ( 2 und 3 ).     

Metallorganische Verbindungen mit N-substituierten 3-Hydroxy-2-methyl-4-pyridon-Liganden: quadratisch-planare Rhodium(I)-, Iridium(I)- und Palladium(II)-Komplexe

Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)₂MCl]₂ (M = Rh, Ir) or [(cod)RhCl]₂ with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L₂M(O–O′)]. Compounds of this type are also available from reactions of [(OC)₂Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)₂Rh(C₁₂H₁₀NO₂)] ( 2 ) with cyclooctene affords [(OC)(C₈H₁₄)Rh(C₁₂H₁₀NO₂)] ( 8 ). The palladium complexes [(R₃P)Pd(O–O′)Cl] (R = Et, Bu), [(C₆H₄CH₂NMe₂) · Pd(O–O′)] and [(Et₃P)₂Pd(O–O′)]BF₄ ( 9 – 12 ) were synthesized from [(R₃P)PdCl₂]₂, [(C₆H₄CH₂NMe₂)PdCl]₂ or [(Et₃P)PdCl₂]. The structures of the N-methyl compounds [(OC)₂Rh(C₇H₈NO₂)] ( 1 ) and [(Ph₃P)Pd(C₇H₈NO₂)Cl] ( 9 ) were determined by single crystal X-ray diffraction.     

CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

Kupfer(I)-jodid-Reagenspapier und Fluorescenz-Thermochromie

Zusammenfassung Zahlreiche aromatische und aliphatische Stickstoffbasen bilden mit Kupfer(I)-jodid fluorescierende Verbindungen, die bei Abkühlung in flüssigem Stickstoff ihre Fluorescenzfärbung ändern. Zur analytischen Auswertung dieses Phänomens wurde ein Reagenspapier entwickelt.Verff. sind der Deutschen Forschungsgemeinschaft, dem Fonds der chem. Industrie und der Wiss. Gesellschaft Saar e.V. für die Förderung dieser Untersuchungen zu Dank verpflichtet.     

Zur Reaktion der Alkin-Kupfer(I)-Komplexe [CuX(S-Alkin)] (X = Cl,Br, I; S-Alkin = 3,3,6,6-Tetramethyl-1-thia-4-cycloheptin) mit dem Chelat-Liganden N,N,N′,N′-Tetramethylethylendiamin (tmeda)

Organometallic Compounds of Copper. XVII. On the Reaction of the Alkyne-Copper(I) Complexes [CuX(S-Alkyne)] (X = Cl, Br, I; S-Alkyne = 3,3,6,6-Tetramethyl-1-thiacyclohept-4-yne) with the Chelate Ligand N,N,N′,N′-Tetramethylethylendiamine (tmeda) The alkyne copper(I) chloride complex [CuCl(S-Alkyne)]_n ( 2 a ) (S-Alkyne = 3,3,6,6–tetramethyl-1-thiacyclohept-4-yne) adds tetramethylethylene diamine (tmeda) to form the mononuclear compound [CuCl(S-Alkyne)(tmeda)] ( 4 ). The alkyne copper halide complexes [CuBr(S-Alkyne)]_n ( 2 b ) and [CuI(S-Alkyne)]_n ( 2 c ) react with tmeda to yield the complex salts [Cu(S-Alkyne)(tmeda)]⁺ [CuX₂(S-Alkyne)]^– (X = Br ( 5 a ), X = I ( 5 b )). X-ray diffraction studies on all new compounds 4 and 5 reveal distorted tetrahedral coordination of the copper atom in complex 4 and trigonal-planar coordinated copper atoms in the cations and anions of the ionic compounds 5 .     

Kupfer(II)-Komplexe mit 2,2′-Dihydroxychalkonen

Copper(II) complexes with 2,2-dihydroxychalkones have been prepared in aqueous alcohol medium and characterised by the elemental analysis. They have 11 stoichiometry and i.r spectra show the involvement of the OH and C=O groups in the bond formation. These copper(II) complexes show magnetic moments in the range of 1.53–1.98 _B and are insoluble in common organic solvents. In view of the magnetic data, solubility and electronic spectral evidences, an extended polymeric structure has been proposed for these complexes.     

Kupfer(II)-Komplexe von N-Benzoyl-O-methyl-N′-phenyl-isoharnstoffen

Copper(II) Complexes of N-Benzoyl-O-methyl-N′-phenyl-isoureas By reaction of N-benzoyl-N′-(p-nitro/p-bromphenyl)thioureas with copper(II)acetate-monohydrate in methanole insoluble copper(I)precipitates have been obtained, from which filtrates bis[N-benzoyl-O-methyl-N′-(p-nitrophenyl)-isoureato]copper(II) 1 and bis[N-benzoyl-O-methyl-(p-bromphenyl)-isoureato]copper(II) 2 were isolated. The moleculare structure of 1 with planar trans coordination has been determined by single crystal X-ray diffraction methods. The N-benzoyl-O-methyl- N′-(o-nitrophenyl)-isourea 3 and N-benzoyl-O-methyl-N′-(p-bromphenyl)-isourea 4 have been prepared by reaction of the corresponding N-benzoyl-N′-phenyl-thioureas with mercury(II)acetate in methanolic solution. The molecular structure of 3 has been determined by single crystal X-ray diffraction methods. The NH-tautomeric form is stabilized by a bifurcated intramolecular hydrogen bond to an oxygen atom of the o-nitro group and the benzoyl oxygen atom. XPS, NMR and mass-spectrometric investigations also confirm the structures.     

Reaktion von Phlorein mit Kupfer(II)-ionen und deren elektrophile Substitution mit Konkurrenzkationen

Zusammenfassung Die vorliegende Arbeit behandelt die Reaktion von Phlorein mit Kupfer(II). In äquimolaren Lösungen kommt es im p_H-Bereich 4,5 bis 8,2 zur Bildung eines Komplexes im Verhältnis der Komponenten 11. Die scheinbare Stabilitätskonstante entspricht beipH4,18 dem Wert logK _1,1= =5,1±0,1 und bei p_H 5,88 dem Wert log K_1,1=5,4±0,1. Bei einem mehr als zehnfachen Überschuß von Cu²⁺-Ionen ist es besonders in alkalischem Medium möglich, eine Komplexbildung mit erhöhter Anzahl koordinierter Metallionen anzunehmen.Mit Hilfe elektrophiler Substitution des Kupfers durch andere Kationen wurde Phlorein als analytisches Reagens für eine Reihe zwei- und einwertiger Kationen charakterisiert.

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Reaction of phlorein with copper(II) Ions and their electrophilic substitution with competing cations

Summary The present study deals with the reaction of phlorein with copper(II). In equimolar solutions and in the p_H range 4.5 to 8.2, there results a complex in which the components are in the ratio 11. The apparent stability constant at p_H 4.18 corresponds to the value log K_1,1=5.1±0.1 and at p_H 5.88 the value is log K_1,1=5.4±0.1. In the presence of a more than 10-fold excess of Cu²⁺ ions it is possible, especially in alkaline medium, to assume a complex formation with an increased number of coordinated metal ions.With the aid of electrophilic substitution of the copper by other cations, phlorein was characterized as an analytical reagent for a number of di- and monovalent cations.

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Symbolverzeichnis M Verdrängungskation - X Bezeichnung von Phlorein - [ ] Gleichgewichtskonzentrationen - analytische Gesamtkonzentrationen - g Anzahl koordinierter Metallionen - n Bjerrumsche komplexbildende Funktion - k _g stufenweise Stabilitätskonstante einesg-Komplexes - K _g totale Stabilitätskonstante einesg-Komplexes - K Gleichgewichtskonstante der Verdrängungsreaktion - Kd Dissoziationskonstante eines Cu²⁺-Komplexes - Proportionalitätskonstante der Ilkovi-Gleichung - Id polarographischer Grenzstromwert - E Potentialwert eines polarographischen Grenzstromes - R Variationsspannweite - (%) Variationskoeffizient in Prozent - (%) Relativfehler in Prozent - A C _X/C _Cu - B C _Cu/C _X     

Dialkylamino-bis(trimethylsilyl)amino-chlorborane und ihre Reaktion mit Natrium-bis(trimethylsilyl)amid

Zusammenfassung Verbindungen des Typs R₂NBCIN(Sime ₃)₂ ^* (R=C₂H₅,ⁱC₃H₇, C₆H₁₁, C₆H₅) bleiben bis zu hohen Temperaturen beständig. Sie reagieren jedoch mit NaN(Sime ₃)₂ unter Übertragung einer Methylgruppe von einem Silicium-zu einem Boratom zu N,N-Bis(trimethylsilyl)-tetramethylcyclodisildiazan und R₂NBmeN(Sime ₃) (R=C₂H₅,ⁱC₃H₇).

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Compounds of the type R₂NBClN(Sime ₃)₂ ^* were prepared. (R=C₂H₅,ⁱC₃H₇, C₆H₁₁, C₆H₅. They do not show any tendency to condense thermally under elimination of trimethylchlorosilane. When these silylaminoboranes were allowed to react with NaN(Sime ₃)₂, complicated rearrangements were observed. The compounds in which R=C₂H₅ orⁱC₃H₇ rearranged under formation of N,N-bis(trimethylsilyl)-tetramethylcyclodisildiazane and R₂NBmeN(Sime)₂. In this reaction a migration of a methyl group from silicon to boron occurs.

     

Alternativ-Liganden. XXIV. Rhodium(I)-Komplexe mit P-Donor-und Sn- bzw. B-Akzeptor-Liganden

Alternative Ligands. XXIV. Rhodium(I) Complexes with P-Donor and Sn- or B-Acceptor Ligands Donor/acceptor ligands of the type Me₂PCH₂CH₂SnMe₃ (1) , (Me₂PCH₂CH₂)₂SnMe₂ (2) , and Me₂PCMe=CMeBMe₂ (3) , respectively, have been prepared by hydrostannlation of Me₂PVi with Me₃SnH or Me₂SnH₂ and by a multistep synthesis via Na[Me₃BH], Na[Me₃BC?;CMe] using Me₂PCI as partner, respectively. The new ligands were used to produce the Rh(I) complexes RhCI(CO)(Me₂PCH₂CH₂SnMe₃)₂ (5) , RhCI(CO)(Me₂PCH₂CH₂)₂SnMe₂ (7), and RhCI(CO)(Me₂PCMe=CMeBMe₂)₂ (8) by reactions of Rh(CO)₂CH₂ (4) with the corresponding ligands. In addition, the VASKA type compounds RhCI(CO)(Me₂PVi)₂ (6) and RhCI(CO)(PMe₃)₂ were prepared in order to test an alternative route to 5 or to from the known adduct RhCI(CO)(PMe₃)₂. BBr₃ (9) . RhBr(CO)(PMe₃)₂ (10) and the binuclear system [RhBr(CO)PMe₃]₂ (11) were identified spectroscopically after working up the 1:1 reaction mixture of RhCI(CO)(PMe₃)₂ and BBr₃. Reasonable pathways are suggested for their formation. ?Metallbase”?/acceptor interaction show up, on the one hand, in following reactions in case of the ligands with Sn acceptors, on the other hand, in significant changes of spectroscopic data for 8 . New compounds of sufficient stability were characterized by analytical (C, H) and spectroscopic (MS, IR. NMR) investigations.     

Matrix-Untersuchungen zu monomerem Kupfer(I)-chlorid und seinen Komplexen mit N2 und PN IR-spektroskopische Nachweise und ab-initio Rechnungen

Matrix-Investigations on Monomeric Copper(I) Chloride and its Complexes with N₂ and PN Ligands. IR Spectroscopic Results and ab-initio Calculation In solid argon the reaction of monomeric CuCl with N₂ yields ClCuN₂. On the basis of two absorptions in the ir-spectrum and their corresponding isotopic shifts (_14/15N) and with the help of a normal coordinate analysis, linearity of the molecule has been deduced. These results are confirmed by large scale ab-initio Calculations (CPF, MP2). Reaction of monomeric CuCl with molecular PN under matrix condition is shown to give rise to new absorptions in the IR spectrum which arev assigned to a linear molecule ClCuNP.     

Einkernige und zweikernige Kupfer(I)‐Komplexe vom Typ LCuCl,LCu2Cl2 und LCu2ClX [L = P(C6H4CH2NMe2)3; X = Br,I]

The title compounds 3‐5 are accessible by treatment of P(C₆H₄CH₂NMe2)₃( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C₆H₄CH₂NMe2)₃]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C₆H₄CH₂NMe2)₃]Cu₂Cl₂ ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C₆H₄CH₂NMe2)₃]Cu₂ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, ¹H‐, ¹³C{¹H}‐ and ³¹P{¹H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å ³ and Z = 4 with 4053 observed unique reflections; R₁ = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P2₁/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; ³ and Z = 4 with 9021 observed unique reflections; R₁ = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu₂Cl₂ segment resembles to a building block which is set up by a contact ion pair consisting of Cu⁺ and [CuCl₂]^‐ , respectively.     

Darstellung und Kristallstrukturen von neutralen und kationischen Kupfer(I)-Gemischtligandkomplexen mit Derivaten des Biimidazols und Triphenylphosphan

Preparation and Crystal Structures of Neutral and Cationic Copper(I) Mixed Ligand Complexes with Triphenylphosphane and Derivatives of Biimidazole Eight triphenylphosphanecopper(I) complexes with bibenzimidazole, tetramethylbiimidazole or tetrahydrobiimidazole were prepared and characterized so far as possible by elemental analysis, IR, ¹H-NMR and ³¹P-NMR spectra. The crystal structures of two complexes with bibenzimidazole were determined. [Cu(bbimH₂)(PPh₃)₂]Cl · CH₂Cl₂: Reaction of CuCl with bibenzimidazole in fused triphenylphosphane or [CuCl(PPh₃)₃] with bibenzimidazole in CH₂Cl₂. Space group P 1, Z = 2, 6440 observed independent reflections, R = 0.064 for refletions with I > 2σ(I). Lattice parameters at 203 K: a = 983.6; b = 1348.9; c = 1805.5 pm; α = 77.24; β = 80.90; γ = 85.81°. The crystal structure is built up by monomeric molecules with distorted tetrahedral coordination of the copper atom (CuN₂P₂) and bibenzimidazole as bidentate ligand. The chloride ion is linked by H-bonds with the NH groups of the bibenzimidazole. [{Cu(PPh₃)₂}₂(μ-bbim)] · 2 CH₂Cl₂: Reaction of [CuCl(PPh₃)₃] with the dipotassium salt of bibenzimidazole in CH₃OH/CH₂Cl₂. Space group P 1, Z = 1, 7192 observed independent reflections, R = 0.057 for reflections with I > 2σ(I). Lattice parameters at 203 K: a = 1334.1; b = 1386.8; c = 1443.7 pm; α = 107.51; β = 103.35; γ = 113.74°. The crystal structure is built up by centrosymmetric molecules with distorted tetrahedral coordination of the copper atoms (CuN₂P₂) and bibenzimidazolate(2–) as tetradentate bridging ligand.     

Quecksilberverbindungen mit Cyancarbanionen. I. Synthese und Kristallstruktur von Diquecksilber(I)-bis(tricyanmethanid)

Mercury Compounds with Cyancarbanions. I . Synthesis and Crystal Structure of Dimercury(I)-bis(tricyanmethanide ) With the triclinic unit cell, space group P1 , with the lattice constants a = 5.2794(1) Å, b = 9.9279(1) Å, c = 11.3376(2) Å, α = 71.004(4)°, β = 76.459(2)° and γ = 74.601(4)° are two formula units. The three-dimensional network, which characterizes the structure, results from dimercury(I) ions with sp³ hybridization, which form beside the homonuclear metal bonding three covalent bonds to cyanonitrogen atoms. The tricyanmethanide ion acts by losing symmetry as a tridentate ligand.     

Isothiocyanat-Komplexe von Kupfer (II) mit quadratisch-planarer und tetragonal-pyramidaler Koordination: Struktur,Phasenumwandlungen und Redoxverhalten

Isothiocyanate Complexes of Copper(II) with Square-Planar and Tetragonal-Pyramidal Coordination: Structure, Phase Transitions, and Redox-Properties In dependence on the kind and size of the counter-cations Cu²⁺-ions form isothiocyanate complexes with different coordination number and geometry. The structures of compounds with square-planar coordination [(NEt₄)₂[Cu(NCS)₄] · CHCl₃ (brown): Space group 14/mmm, Z = 2; a = 1204.3(2) pm, c = 1154.2(3) pm] and with tetragonal-pyramidal polyhedra [(NEt₄)₃[Cu(NCS)₅] · SM (green, SM: unidentified solvent molecule): Space group P2₁/c, Z = 4; a = 1154.2(6) pm, b = 2291.6(10) pm, c = 1739.9(9) pm, ß = 95.98(5)°] are reported. The green complex transforms into a brown compound at room-temperature; the transformation is (partly) reversibly. Solutions of NCS-anions and Cu²⁺ are redox unstable. The structure of a resulting product: (PPh₄)₂[Cu₂(NCS)₂] [Space group C2/c, Z = 4; a = 1235.4(1) pm, b = 1347.1(2) pm, c = 2953.4(11) pm, ß = 99.36(2)°] with Cu(I) dimers and two bridging NCS^- ligands is also reported.