Synthese und Struktur porphinoider Nickel‐Komplexe mit axial orientierten Seitenketten

Synthesis and Structure of Porphine‐type Nickel Complexes Containing Axially Oriented Sidechains The structure of (±)‐[1, 11‐dimethoxy‐10 H‐HDP (2‐)]nickel ( 3 ), the product of the thermodynamically controlled addition of methanol to [6 H‐HDP]nickel‐bis‐(tetrafluoroborate) ( 1 ), was determined by X‐ray analysis. The two methoxy groups in 3 are cis ‐oriented. The syntheses and spectroscopic properties of [1, 11‐diethoxy‐10 H‐HDP (2‐)]nickel ( 5 ), [1, 11‐dineopentyloxy‐10 H‐HDP (2‐)]nickel ( 6 ) as well as the bridged complexes [1, 11‐pentamethylenedioxy‐10 H‐HDP (2‐)]nickel ( 4 ) and [1, 11‐( E )‐2,3‐(dimethyl‐2‐butenylenedioxy)‐10 H‐HDP (2‐)]nickel ( 7 ) are described. Reaction of 1 with bromide ions or 4‐methylpyridine leads to the formation of the corresponding hexacoordinated, paramagnetic complexes dibromo [6 H‐HDP]‐nickel (II) ( 8 ) and bis (4‐methylpyridine)[6 H‐HDP]nickel‐bis (tetrafluoroborate) ( 9 ).