Eine Reihe von Schiffbase-Komplexen von Platin(II), Palladium(I1) und Kupfer(I1) 1 -4 wird aus Glycinato-Chelatkomplexen und Amidacetalen erhalten. Die Struktur der Verbindungen wird spektroskopisch, die von Cl(n-Bu,P)PtO,C -CH, -N = CHNMe, (3a) durch Rontgenstrukturanalyse bestimmt. Bei trans-Bis(glycinato)platin(II) wird mit DMF auch Reaktion an der a-Methylengruppe eines Glycinat-Liganden unter Bildung eines Serinderivats als Liganden (5) beobachtet, wobei der Bis(Schiffbase)-Komplex 2a als Zwischenprodukt isoliert werden kann. Amidacetale greifen (Glycinato)platin(II)-Komplexe primar stets an der Aminogruppe an, erst im zweiten Schritt kann die Reaktion an der a-Methylengruppe des koordinierten Schiffbase-Liganden erfolgen.A series of Schiff base complexes of platinum(II), palladium(II), and copper(I1) 1 -4 has been obtained from glycinato chelate compounds and amide acetals. The structure of the complexes has been determined by their IR and NMR spectra, that of 3a by an X ray structure analysis. With trans-bis(glycinato)platinum(II) also reaction with DMF at the a-methylene group of a glycinate ligand has been observed to give a serine derivative as ligand (5), the Schiff base complex 2a being isolated as intermediate. The first step of these reactions always is an attack of the amide acetal at the amino group; the coordinated and activated Schiff base ligands may also react at the a-rnethylene group. *) Die in Lit . 5 ) beschriebenen Umsetzungen von (n-Bu3P)Pt(Cl)(glycinat) mit Aldehyden und Alkylierungsmitteln konnten wir unter den angegebenen Bedingungen nicht mehr reproduzieren.
Abstract The infrared spectra (200-4000 cm-1) of trans- and cis-Pt(NX2CH2COO)2 (X = H, D), trans- and cis-PtCl2(NH2CH2COOH)2, trans-PtCl2(NH2CH2CO2Et)2, cis-PtCl2(NX2CH2CO2Et)2, cis-PtCl2(NX2CH2NXCH2CO2Et)2 (X = H, D) and cis-PtY2(NH2CH2NHCH2CO2Et)2 (Y = Br, I) including 15N derivatives have been studied. There is no appreciable change of vibrational frequencies for corresponding cis- and trans- complexes which could be attributed to the trans-influence of different ligands. Due to lower symmetry most of the absorptions of the cis-complexes are split into doublets compared with the trans-compounds.
Die Glycinato‐Chelatkomplexe (I), (IV) und (VI) reagieren mit den Amidacetalen (II) unter elektrophilem Angriff nicht am α‐C‐Atom des koordinierten Glycins, sondern am N‐Atom, wobei die Schiffsche Basen‐Komplexe (III), (V) und (VII) gebildet werden.
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