Magnetische Untersuchungen an Komplexen von La(III), Pr(III) und Nd(III) mitSchiffschen Basen

Specific magnetic susceptibilities (_s) of several newly synthesized chelates of some of the lanthanons [La(III), Pr(III) and Nd(III)] are reported. These derivatives are of the general type,Ln(O-i-C₃H₇)_3–n (C₆H₅CHNRO) _n [where,Ln=La(III), Pr(III) or Nd(III);n=1 or 2 and R=CH₂CH₂, CH₂CHCH₃ or C₆H₄] and have been prepared by the reaction of the alkoxides of the lanthanons withSchiff bases such as benzylidene-2-hydroxyethylamine (C₆H₅CHNCH₂CH₂OH), benzylidene-2-hydroxy-n-propylamine (C₆H₅CHNCH₂CHOHCH₃) and benzylidene-o-aminophenol (C₆H₅CHNC₆H₄OH) in different molar relations in dry benzene.The resulting crystalline derivatives are non-volatile, light to deep yellow or blackish in colour. These tend to polymerize on keeping as shown by their insoluble nature and higher melting points, the polymerisation possibly occurring by the intermolecular coordination through oxygen atoms as reported earlier¹.UsingGouy method², the bis-isopropoxy mono-Schiff base and mono-isopropoxy bis-Schiff base complexes of La(III) have been shown to be diamagnetic, with _s values being in the range of –0.32 to –0.45×10^–6 and –0.39 to –0.55×10^–6 c.g.s. units at 305 K respectively.In the remaining derivatives, Pr(O-i-C₃H₇)_3–n (C₆H₅CH NRO) _n and Nd(O-i-C₃H₇)_3–n (C₆H₅CHNRO) _n (where,n=1 or 2 and R=CH₂CH₂, CH₂CHCH₃ or C₆H₄) the magnetic moment values range between 3.25 to 3.32 and 3.30 to 3.33 _B respectively indicating their paramagnetic nature.     

Cyanato-Kupfer(II)-Komplexe mit organischen Liganden. VI. Darstellung,Elektronen- und Infrarotspektren einiger Cyanato-Kupfer(II)-Komplexe mit Liganden der Anilingruppe

Cyanato-Copper(II) Complexes with Organic Ligands. VI. Preparation, Electronic and Infrared Spectra of Some Cyanato-Copper(II) Complexes with Ligands from Aniline Group Complexes of the type Cu(NCO)₂L₂ were prepared (L see “Inhaltsübersicht”), and their electronic spectra in the solid state and in solution, as well as their infrared spectra were recorded. The spectral results indicate that these complexes have — except Cu(NCO)₂(o-Tol)₂ – trans planar Cu(NCO)₂ L₂ molecules with the cyanate groups bonded through the nitrogen atom. In acetone and methanol solutions these molecules are completed with two solvent molecules to form pseudooctahedral species with different axial distortion. The complex Cu(NCO)₂(o-Tol)₂ displays bridging N-coordinated cyanate groups and thus a polymeric structure. In the acetone, methanol and chloroform solution does it exhibit no coordinated solvent molecules. The complexes with L = m- and p-toluidin in the chloroform solution are revealed as planar Cu(NCO)₂L₂ molecules.     

Phenyl-diphenyltriazen-chrom(III)-Komplexe

Phenyldiphenyltriazene Chromium Complexes Diphenyltriazene complexes of chromium(III) have been prepared. In the series Ph₃Cr · 3 THF, Ph₂Cr(N₃Ph₂) · 2 THF, PhCr(N₃Ph₂)₂ · THF, and Cr(N₃Ph₂)₃, the thermal and hydrolytical stability is strongly enhanced. It is supposed, that the triazenido anions act as chelating ligands.     

Trägerfixierte Organometallkomplexe. VI. Charakterisierung und Reaktivität Polysiloxan-gebundener (Ether-phosphan)ruthenium(II)-Komplexe

Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes The ligands PhP(R)CH₂D [R = (CH₃O)₃Si(CH₂)₃; D = CH₂OCH₃ ( 1b ); D = tetrahydrofuryl ( 1c ); D = 1,4-dioxanyl ( 1d )] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)₄ to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl₂Ru(CO)₂(P ～ O)₂ ( 3b ) and HRuCl(CO)(P ～ O)₃ ( 5b ) were treated with NaBH₄ to form cis,cis,trans-H₂Ru(CO)₂(P ～ O)₂ ( 4b ) and H₂Ru(CO)(P ～ O)₃ ( 6b ), respectively (P ～ O = η¹-P coordinated; = η²- coordinated). Addition of Si(OEt)₄ and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b ′, 6b ′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by ²⁹Si CP-MAS NMR spectroscopy. 4b ′ reacts with carbon monoxide to form Ru(CO)₃(P ～ O)₂ ( 7b ′). Chelated polysiloxane-bound complexes Cl₂Ru( )₂ ( 9c ′, d ′) and Cl₂Ru( )(P ～ O)₂ ( 10b ′, c ′) have been synthesized by the reaction of 1b–c with Cl₂Ru(PPh₃)₃ ( 8 ) followed by a copolymerization with Si(OEt)₄. The polysiloxane-bound complexes 9c ′, d ′ and 10b ′, c ′ react with one equivalent of CO to give Cl₂Ru(CO)( )(P ～ O) ( 12b ′– d ′). Excess CO leads to the all-trans-complexes Cl₂Ru(CO)₂(P ～ O)₂ ( 14b ′– d ′), which are thermally isomerized to cis,cis,trans- 3b ′– d ′. The chemical shift anisotropy of ³¹P in crystalline Cl₂Ru( )₂ ( 9a , R = Ph, D = CH₂OCH₃) has been compared with polysiloxane-bound 9d ′ indicating a non-rigid behavior of the complexes in the matrix.     

Tris(triphenylphosphan)nickel(0)-Komplexe mit Nitril-Liganden

Tris(triphenylphosphane)nickel(0) Complexes with Nitrile Ligands . Synthesis, properties and reaction behaviour of (Ph₃P)₃Ni(η¹-NCR) (R = PhCH₂, 2-MeC₆H₄, Me₃Si) complexes as well as the X-ray structure of (Ph₃P)₃Ni(η¹-NCSiMe₃) are described. With NC(CH₂)_nBr (n = 1, 2) instead of the analogous nitrile complexes (Ph₃P)₂NiBr₂ and CH₃CN or C₂H₅CN respectively are formed.     

1,4-Diazabuta-1,3-dien-N-Sulfinylamin-Nickel(0)-Komplexe

1,4-Diazabuta-1,3-Diene-N-Sulfinylamin Nickel(0) Complexes Synthesis, properties, and reactions of 1,4-diazabuta-1,3-diene-N-sulfinylamine nickel(0) complexes are described. The highly coloured and extremely air and moisture sensitive nickel(0) complexes have been characterized by means of i.r. and ¹H n.m.r.spectroscopy. The N-sulfinylamine ligands are η²-(S,N)-side on coordinated.     

Zur Kenntnis der Mono-ethylendiamin-cobalt(III)-Komplexe

Preparation and Properties of Mono-ethylenediaminecobalt (III) Complexes [Co(N₃)₃en]₂ and [CoCl₂(H₂O)₂en]Cl are useful starting materials for the preparation of numerous mixed-ligand complexes of Co^III containing one molecule of ethylenediamine. The preparation and the properties of a series of new compounds are described. Improved methods for the preparation of known complexes are given (see Inhaltsübersicht).     

Benzylnickel(II)-Komplexe und ihre Reaktionen

Benzyl Nickel(II) Complexes and their Reactions By the oxydative addition of p-substituted benzyl chlorides to (Ph₃P)₂Ni(C₂H₄) at ?20°C the violet nickel(II) complexes (Ph₃P)₂Ni(p-CH₂C₆H₄R)Cl (R ? CN, COOH, CH₃, Cl) are, formed. In water containing solutions the carbonic acid (Ph₃P)₂Ni(p-CH₂C₆H₄COOH)Cl is rearranged to the corresponding p-methylbenzoate. With carbon dioxide the complexes (Ph₃P)₂Ni(p? CH₂C₆H₄R)Cl react like Grignard compounds. Diphenyl ethine and butadien-1,3 are inserted in the Ni—C bond at room temperature. Substituted nickel-σ-vinyl or π-allyl complexes are obtained. The reactivity of the nickel-σ-benzyl compounds is compared with that of other nickel(II)-alkyl compounds.     

Uran(VI) und Plutonium(VI)

Ohne Zusammenfassung     

Tris-(salicylaldehydato)-Komplexe einiger Seltenerdelemente mit o-Hydroxybenzoylhydrazid

Complexes of some rare earth elements (La, Ce^III and Y) with salicylaldehyde and o-hydroxybenzoylhydrazide of formula La(o-Bh)₃(Sald)₃·4 H₂O, La(o-Bh)₆(Sald)₃, Ce(o-Bh)₆(Sald)₃, and Y(o-Bh)₅(Sald)₃·2 H₂O were isolated. These complexes were identified by elementary analysis and characterized by X-ray crystallography, thermogravimetric analysis and IR absorption spectroscopy. Coordination sites of o-hydroxybenzoylhydrazide are discussed with reference to the characteristic IR absorption bands of the CONHNH₂ and phenolic OH groups.

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o-Bh o-Hydroxybenzolhydrazid - Stald Salicylaldehyd