ISSN:
0075-4617
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Metal Complexes with Tetrapyrrole Ligands, X1). - Synthesis and Configuration of Further (a,y-Dimethyl-a,y-dydrooctaethy1porphinato)metal ComplexesStarting from metal complexes 1a, 1f-1m of octaethylporphin [(OEP)MXY (M = Zn, Pd, Pt, Ga, In, Mn, Ti, V, Si)] another series of (a,y-dimethyl-a,y-dihydrooctaethylporphinat0)- metal complexes 2f-2n [(OEPMe2)MXY (M = Pd, Pt, Ga, In, Mn, Ti, V, Si, Sn)] has been prepared and spectroscopically characterized. Reductive methylation of (0EP)MXY 1f-1m yields 2f-2m. The axial ligands X and Y are substituted under the reaction conditions if ligands other than terminal oxide ligands are present. (OEPMeZ)Sn(OAc)z (2n) is formed from SnClz and (OEPMe2)Hz (3) prepared in situ. Comparison of the 1H-NMR spectra of the complexes 2a-2n demonstrates the syn-axial configuration of C-cc and C-y in (OEPMe2)MXY 2. The methyl groups and the terminal oxide ligand are syn-axial (exo) in (0EPMe2)Ti=O (2k).
Notes:
Ausgehend von Metallkomplexen 1a, 1f-1m des Octaatlylporphins [(OAP)MXY (M = Zn, Pd, Pt, Ga, In, Mn, Ti, V, Si)] wurden weitere (a,y-Dimethyl-a,y-dihydrooctaathylporphinato)metallkomplexe2f-2n [(OxPMe2)MXY (M = Pd, Pt, Ga, In, Mn, Ti, V, Si, Sn)] dargestellt und spektroskopisch charakterisiert. Die reduzierende Methylierung von (OAP)MXY 1f-1m liefert 2f-2m. Die axialen Liganden X und Y werden dabei ausgetauscht, soweit andere als terminale Oxid-Liganden vorhanden sind. (OAPMez)Sn(OAc)z (2n) entsteht aus SnC12 und in situ bereitetem (0APMez)Hz (3). Vergleich der IH-NMR-Spektren der Komplexe 2a-2n deutet auf die syn-axiale Konfiguration von C-cc und C-y in (OAPMe2)MXY 2 hin. (0APMez)Ti=O (2k) tragt die Methylgruppen und den terminalen Oxid-Liganden in syn-axialer (exo-) Position.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.197419740705
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