Spektroskopische Untersuchung des Oxodiperoxooxalatomolybdat(VI)-Anions

Spectroscopic Investigation of the Oxodiperoxooxalatomolybdate(VI)Anion The infrared and electronic spectra of K₂[MoO(O₂)₂C₂O₄] are recorded and interpreted. The characteristics of the metal-oxygen and metal-peroxide bonds are discussed and some comparisons with related species are made.     

1,2-Bis-triphenylphosphoranylidenamino-äthan als zweizähniger Ligand in Übergangsmetallkomplexen

1,2-Bis-(triphenylphosphorane-ylidene-amino)ethane as a Bidentate Ligand in Transition Metal Complexes The reactions of Ph₃P?N? C₂H₄? N?PPh₃ with transition metal halogenides MX₂ give according to eq. (1) novel bisiminophosphorane complexes of the type M(Ph₃PNC₂H₄ NPPh₃)X₂ (M ? Co, X ? Cl 1 a , Br 1 b , J 1 c ; M ? Ni, X ? Cl 2 a , Br 2 b , J 2 c , M ? Hg, X ? Cl 3 , M ? Cd, X ? Cl 4 ). The preparation, properties, magnetic moments, and structure of the new complexes are reported     

Spektroskopische Untersuchung von Ammonium-oxodiperoxoamminovanadat(V)

The infrared and electronic spectra of NH₄[VO(O₂)₂NH₃] are recorded and interpreted. The results are discussed and some comparisons with related species are made.

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2-Bis(carboxymethyl)-amino-5-hydroxy-terephthalsäure als ambifunktioneller Ligand in Eisen(III)-Komplexen

2-Bis(carboxymethyl)-amino-5-hydroxy-terephthalic Acid as an Ambifunctional Ligand in Iron(III) Complexes From steric reasons the anthranilic acid -N,N-diacetic acid group and the salicylic acid group of 2-bis(carboxymethyl)-amino-5-hydroxy-terephthalic acid (H₅C) cannot coordinate to the same central atom. With iron(III) H₅C forms the mononuclear complex (HC)Fe(OH)^2?, the central atom is fixed to the anthranilic acid N,N-diacetic acid group. In a weak acid medium (HC)Fe(OH)^2? is converted into the binuclear species (HC)Fe(C)Fe(OH)^4? which is of a deep red colour. In this complex the anion C^5?has the function of a bridging ligand coordinating both by the anthranilic acid-N,N-diacetic acid group and by the salicylic acid group. The complex formation in the ternary system iron(III)/nitrilo triacetic acid/5-sulfo salicylic acid may be used as model for the dimerisation of the anion (HC)Fe(OH)^2?.     

Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe. VIII. Zweikernige Cobaltkomplexe mit dem Dianion des Bis(cyclopentadienyl)methans und des Bis(tetramethylcyclopentadienyl)dimethylsilans als Brückenliganden

Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes. VIII. Dinuclear Cobalt Complexes with the Dianion of Bis(cyclopentadienyl)methane and Bis(tetramethylcyclopentadienyl)dimethylsilane as Bridging Ligands The dinuclear cobalt complex [CH₂(C₅H₄)₂][Co(CO)₂]₂ ( 4 ) which is obtained from [Co(CO)₄I] ( 2 ) and Li₂[CH₂(C₅H₄)₂] ( 3 ) in 75% yield reacts with PMe₃, PiPr₃, P₂Me₄, Me₂PCH₂CH₂PMe₂ and (EtO)₂POP(OEt)₂, to the compounds 5–9 substituting one CO ligand per cobalt atom. Oxidative addition of CH₃I to [CH₂(C₅H₄)₂][Co(CO)(PMe₃)]₂ ( 5 ) leads to the formation of the dinuclear cobalt(III) complex [CH₂(C₅H₄)₂][Co(COCH₃)(PMe₃)I]₂ ( 11 ). The reaction of 4 with iodide generates [CH₂(C₅H₄)₂][Co(CO)I₂]₂ ( 12 ) which with PMe₃, P(OMe)₃, P(OiPr)₃, and CNMe reacts under CO substitution to [CH₂(C₅H₄)₂][Co(L)I₂]₂ ( 13–16 ) and with PMe₂H to {[CH₂(C₅H₄)₂][Co(PMe₂H)₃]₂}I₄ ( 17 ). The electrophilic addition reactions of NH₄PF₆ and CH₃I to [CH₂(C₅H₄)₂][Co(PMe₃)₂]₂ ( 20 ) produce the complex salts {[CH₂(C₅H₄)₂][CoR(PMe₃)₂]₂}X₂ ( 21 : R = H; 22 : R = CH₃). From 22a (X = I) and LiCH₃ the dinuclear tetramethyldicobalt compound [CH₂(C₅H₄)₂] · [Co(CH₃)₂(PMe₃)]₂ ( 23 ) is obtained which further reacts, via the intermediate 24 , to the chiral complex {[CH₂(C₅H₄)₂] · [CoCH₃(PMe₃)P(OMe)₃]₂}(PF₆)₂ ( 25 ). The reaction of 20 with C₂(CN)₄ and E- or Z-C₂H₂(CO₂Me)₂ gives the olefin(trimethylphosphine) cobalt(I) derivatives 26 und 27 . The synthesis of the dinuclear compounds 31–38 with [Me₂Si(C₅Me₄)₂]^2? as the bridging unit is also described.     

Spektroskopische Eigenschaften von Bis(imidazol)kupfer(II)diacetat

Summary Electronic and vibrational spectra of bis(imidazol)copper(II)diacetate were investigated in order to obtain a wider insight into the structural properties of this interesting complex compound, which presents high cytotoxic activity. Electronic transitions were investigated by reflectance measurements of the solid and by absorption, using aqueous and methanolic solutions. IR spectra could be interpreted on the basis of the characteristic ligand vibrations. Some information could also be obtained for the Cu-N and Cu-O vibrations. For comparative purposes, the IR spectrum of Cu(imidazol)₄I₂ was also recorded and analyzed.

     

Spektroskopische Untersuchung der Carbonatbildung in Blei(Il)-Oxidschichten

Ohne Zusammenfassung     

Synthesen zweizähniger P‐Donor/Sn‐Akzeptor‐Liganden: Koordinationsstudien mit Cp*Rh(CO)2 und CpRh(C2H4)2

Alternative Ligands. XXXV. Syntheses of Bidentate P‐Donor/Sn‐Acceptor Ligands: Coordination Experiments with Cp*Rh(CO)₂ and CpRh(C₂H₄)₂ Donor/acceptor ligands Me₂Sn(CH₂CH₂PMe₂)₂ ( 1 ) and Me₂Sn(OCH₂PMe₂)₂ ( 2 ) have been prepared by radical reaction of Me₂PVi with Me₂SnH₂ and by substitution of chlorine in Me₂SnCl₂ or of ethoxy groups in Me₂Sn(OEt)₂ by MOCH₂PMe₂ (M = Li, Na) and HOCH₂PMe₂, respectively. 2 cannot be isolated in pure form from the product mixture because, due to condensation reactions, the “ladder structure” [Me₂Sn(OCH₂PMe₂)₂OSnMe₂]₂ ( 3 ) is formed. The molecular structure of 3 was determined by X‐ray diffraction studies of single crystals. Attempts to produce the thiophosphoryl derivative of 3 result in the degradation of the ladder structure giving the thermally labile phosphane sulfide Me₂Sn(OCH₂P(S)Me₂)₂. Ligands 1 and 2 besides Me₂PCH₂CH₂SnMe₃ ( 4 ) have been used for the preparation of rhodium(I) complexes from Cp*Rh(CO)₂ ( 5 ) or CpRh(C₂H₄)₂ ( 10 ) as educts. The thermal reaction of 5 with 4 yields Cp*Rh(CO)PMe₂CH₂CH₂SnMe₃ ( 6 ), that of 5 with 1 a mixture of the mononuclear derivative Cp*Rh(CO) · PMe₂CH₂CH₂SnMe₂CH₂CH₂PMe₂ ( 7 ) and the binuclear complex [Cp*Rh(CO)PMe₂CH₂CH₂]₂SnMe₂ ( 8 ). The related system [Cp*Rh(CO)PMe₂CH₂O]₂SnMe₂ produced by reaction of 5 with 2 can only be detected in solution but, because of some side‐products, was not fully characterized. From 10 and 4 a mixture of mono‐ and disubstituted products, CpRh(C₂H₄)PMe₂CH₂CH₂SnMe₃ ( 11 ) and CpRh(PMe₂CH₂CH₂SnMe₃)₂ ( 12 ), is obtained. Reaction of 1 with 10 yields a mixture of the complexes CpRh(C₂H₄)PMe₂CH₂CH₂SnMe₂CH₂CH₂PMe₂ ( 13 ) and CpRh(Me₂CH₂CH₂)₂SnMe₂ ( 14 ). Some of the NMR data (¹³C, δδ_Sn) of 14 can be interpreted in terms of the expected Rh → Sn interaction. A definite proof by X‐ray diffraction on single crystals, so far, was not possible.