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  • 1
    ISSN: 0044-2313
    Keywords: Thiosemicarbazide Nickel Complexes ; Syntheses ; IR, Electronic Absorption Spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Übergangsmetall-Komplexe mit Thiosemicarbazid-Liganden. XII. Komplexe von NiII mit Benzoylaceton-S-Methylisothiosemicarbazon und N(1)-2-Butyliden-4-oxo-4-Phenyl-N(4)-Salicyliden-S-MethylisothiosemicarbazidDurch Templat-Synthese wird [Ni(HL1)NH3]I (HL1 = Monoanion des dreizähnigen ONN-Liganden Benzoylaceton-S-Methylisothiosemicarbazid) erhalten. Dieser Komplex ergibt mit einem Überschuß von NH4NCS, Pyridin oder Hydrazin die Komplexe [Ni(HL1)NH3NCS] bzw. [Ni(L1)A] (A = Py, N2H4). Die monoanionische Form des Liganden entsteht durch De Protonierung der enolischen Form des Benzoylaceton-Restes, während die dianionische Form durch zusätzliche Deprotonierung der terminalen NH2-Gruppe erhalten wird. Durch Reaktion von [Ni(HL1)NH3]I mit Salicyladehyd wird der NiL2-Komplex erhalten, in dem L2 das Dianion des ONNO-Liganden N(1)-2-Butyliden-4-oxo-4-Phenyl-N(4)-Salicyliden-S-Methylisothiosemicarbazid ist. Alle Komplexe sind diamagnetisch und haben quadratisch-planare Konfiguration, ausgenommen [Ni(HL1)(NH3)NCS], bei dem die IR-Spektren auf quadratisch-pyramidale Struktur weisen. Durch die Absorptionsspektren der Komplexe in Ethanol wird die quadratisch-planare Koordination des NiII belegt.
    Notes: A template synthesis procedure yielded [Ni(HL1)NH3]I, where HL1 is the monoanion of the terdentate ONN benzoylacetone S-methylisothiosemicarbazone ligand. The reaction of this complex with an excess of NH4NCS, pyridine, or hydrazine resulted in the complexes [Ni(HL1)(NH3)NCS] and [Ni(L1)A] (A = Py, N2H4). The monoanionic form of the ligand is obtained by deprotonation of the enolic form of the benzoylacetone moiety, whereas the dianion is formed by additional deprotonation of the terminal NH2 group. Finally, the reaction of [Ni(HL1)NH3]I with salicyladehyde produced the NiL2 complex in which L2 stands for the dianion of the ONNO ligand N(1)-2-butylidene-4-oxo-4-phenyl-N(4)-salicylidene-S-methylisothiosemicarbazide. All complexes are diamagnetic and have a square-planar configuration, except for [Ni(HL1)(NH3)NCS], for which te data of i.r. spectra suggest a square-pyramidal structure. The electronic absorption spectra of the ethanolic solutions of all complexes are characteristic of typical square-planar coordination of nickel(II).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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