Structural and thermal analysis of phosphoramidothioate,phosphorodiamidothioate and N,N′-diphenylphosphorodiamidothioate complexes of Zn(II), Cd(II) and Hg(II)

A new series of complexes of Zn(II), Cd(II) and Hg(II) with phosphoramidothioate (PAT), phosphorodiamidothioate (PDAT) and N,N-diphenylphosphorodiamidothioate (N,N-DPDAT) ligands have been synthesized and studied. The structures of the new compounds are discussed on the basis of their spectroscopic and thermal data. Thermoanalytical studies of these compounds have shown a dependence of the thermal stability on the size of the metal cation; the PAT complexes have greater thermal stability than the others.

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Zusammenfassung Komplexe von Zn(II), Cd(II) und Hg(II) mit Phosphoramidothioat (PAT), Phosphorodiamidothioat (PDAT) und N,N-Diphenylphosphorodiamidothioat (N,N-DPDAT) als Liganden wurden synthetisiert und untersucht. Die Strukturen der neuen Verbindungen werden basierend auf deren spektroskopischen und thermischen Daten diskutiert. Die thermoanalytische Untersuchung dieser Verbindungen hat eine Abhängigkeit der thermischen Stabilität von der Größe der Metallkationen ergeben, und zwar sind die PAT-Komplexe thermisch stabiler als die anderen.

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, , N,N . N,N . . . .

     

Darstellung und Elektronenspektren neuer Trithiocarbonato-Komplexe; Struktur,Eigenschaften und Photoelektronenspektren von Ni(NH3)3CS3 und Zn(NH3)2CS3

Preparation and Electronic Spectra of new Trithiocarbonato Complexes; Structure, Properties, and Photoelectronic Spectra of Ni(NH₃)₃CS₃ and Zn(NH₃)₂CS₃ The complex anions [Zn(CS₃)₂]^2?, [Cd(CS₃)₂]^2?, [Co(CS₃)₃]^3?, [Cr(CS₃)₃]^3?, [As(CS₃)₃]^3?, [Sb(CS₃)₃]^3?, [Bi(CS₃)₃]^3?, [Sn(CS₃)₂]^2?, and [Cu(CS₃)] could be isolated as tetraphenylphosphonium and tetraphenylarsonium salts. From the electronic spectra of the transition metal complexes it follows that the CS ion exhibits, in comparison with other sulfur containing ligands, relatively large Δ-values and only a small nephelauxetic effect (e.g. in [Cr(CS₃)₃]^3?: Δ = 16.0 kK; β₃₅ = 0.57). The trithiocarbonate ion in all the above complexes acts as a bidentate ligand and forms fourmembered ring systems CS₂M. Further it was proved by means of infrared, electronic and photoelectronic spectra that the structure of “Ni(NH₃)₃CS₃” is [Ni(NH₃)₆][Ni(CS₃)₂] whereas Zn(NH₃)₂CS₃ has not such an ionic structure.     

Structural and thermal analysis of silicon isothiocyanates complexes of Fe(III) and Mn(II)

New complexes of Fe(III) and Mn(II) with R_xSi(NCS)_4–x as ligands have been prepared and characterized. The structure of the new compounds are discussed on the basis of their spectroscopic (IR and UV-Vis), magnetic susceptibility and thermal data.

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Zusammenfassung Es wurden neue Fe(III)- und Mn(II)-Komplexe mit Liganden der Formel R_xSi(NCS)_4–x hergestellt und beschrieben. Bei der Diskussion der Struktur dieser neuen Verbindungen wurden spektroskopische (IR, UV), thermische Daten und Daten über die magnetische Suszeptibilität verwendet.

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R_xSi(NCS)_4–x. ( , - ), .

     

Monohalogenobenzoylhydrazones VI. New antimony(III) complexes with monochlorobenzoylhydrazones of 2-furaldehyde, 2-pyrrolaldehyde and 2-thiophenaldehyde as ligands

The antimony(III) trihalides, SbX₃ (X=Cl, Br and I), react with the title ligands to give the compounds SbX₃L, where L=benzoyl- and monochlorobenzoylhydrazones of 2-furaldehyde (FBHH and FClBHH), 2-pyrrolaldehyde (PBHH and PClBHH) and 2-thiophenaldehyde (TBHH and TClBHH). The characterization of the new species was based on their elemental analyses, spectral data (IR and UV-Vis) and thermal studies. The ligands appear to offer two coordination sites (the carbonyl and azomethine groups) and perhaps a third one (the heteroatom of the heterocyclic ring). The thermal decompositions of the studied complexes proceed via one or three stages, the number of stages depending on the nature of both the hydrazones and the halogens. The structures proposed for the investigated complexes are either pseudo- or distorted octahedral.

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Zusammenfassung Antimon(III)-trihalogenide, SbX₃ (X=Cl, Br und I) reagieren mit den Titelliganden und liefern Verbindungen der allgemeinen Formel SbX₃L (L=Benzoylbzw. Monochlorobenzoylhydrazon von 2-Furfuraldehyd (FBHH und FClBHH), von 2-Pyrrolaldehyd (PBHH und PClBHH) und von 2-Thiophenaldehyd (TBHH und TClBHH). Die neuen Verbindungen wurden mittels Elementaranalyse, Spektraldaten (IR und UV) sowie thermischen Untersuchungen beschrieben. Zwei Koordinationsstellen scheinen von den Liganden bevorzugt zu sein: die Carbonylund die Azomethingruppe. Eine dritte könnte das Heteroatom des heterocyclischen Ringes sein. Die thermische Zersetzung der untersuchten Komplexe vollzieht sich in Abhängigkeit von der Natur der Hydrazone und der Halogene in einem oder in drei Schritten. Als Struktur für die untersuchten Komplexe wird eine pseudo-oder verzerrte oktaedrische Struktur vorgeschlagen.

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SbX ₃ (X=Cl, Br, I) - , 2- 2- , SbX ₃ L. , ( ), . , , . . .

     

Electron paramagnetic resonance and magnetic susceptibility of rare-earth hydrazone compounds

The magnetic properties of the rare earth molecular compounds with hydrazone ligands containing Nd³⁺, Gd³⁺, and Yb³⁺ have been investigated by electron paramagnetic resonance (EPR) and magnetization measurements. For the Gd-compound, partially resolved fine structure due to Gd³⁺ and exchange narrowing effects at low temperatures are observed in the EPR spectra, suggesting, consistent with the EPR and dc magnetic susceptibility, weak antiferromagnetic exchange interactions. Paramagnetic behavior sustained down to low temperatures is derived for Yb³⁺ ions, whereas substantial ferromagnetic exchange coupling is inferred for the lighter Nd³⁺ ions, indicating significant variations of the exchange integrals along the lanthanide series. Received 29 April 2002 Published online 31 July 2002