Peculiar reactivity of face to face biscorrle an dporphyrin-corrole with a nickel(II)salt.X-Ray structural characterization of a new nickel(II) bisoxocorrloe.

摘要

New nickel(II) bisoxocorrole complexes have been synthesized and characterized.Two nickel bisoxocorrole isomer complexes are formed in a 1:1 ratio when a biscorrole,where an anthracenyl bridge links the two macrocycles in a face to face arrangement,is metallated by nickel in air.Evidence for th einsertion of an oxo group at one of the meso positions is given by the X-ray structural charactwerization of the Ni_2(BOCA)"cis"isomerwhere BOCA is a bisoxocorrole with an anthracenyl spacer.Conversely,under the same reaction conditions no nickel bisoxocorrole is obtained when biphenylene is the linker of th ebiscorrole system,the major product of the reaction being a bisnickel bisradical species.Only a small amount of a bisnickel hydrooxobiscorrole is isolated in the reaction.A reaction mechanism for both series (anthracenyl an dbiphenylenyl) is given and a comparison of the behavior of the biscorrole system with related derivatives is proposed.