title: From para-Benziporphyrin to Rhodium(III) 21-Carbaporphyrins: Imprinting Rh⋅⋅⋅η(2)-CC, Rh⋅⋅⋅η(2)-CO, and Rh⋅⋅⋅η(2)-CH Coordination Motifs.
abstract: Rhodium(III) para-benziporphyrin alters the fundamental reactivity of the built-in para-phenylene moiety. Due to additional macrocyclic stabilization, a sequence of intramolecular rearrangements are triggered to afford rhodium(III) 21-carbaporphyrin, which incorporates the rhodacyclopropane motif. The peculiar reversible transformations of the bridging methylene unit provide an example of selective and reversible aliphatic C-H bond elimination. Rhodium(III) 21-carbaporphyrin can be oxygenated to rhodium(III) 21-oxy-21-carbaporphyrin, whereas the metal ion interacts with the C(21)-O(25) fragment in an η(2) fashion. This species demonstrates a remarkable axial affinity toward alkenes.
authors.affiliation: Department of Chemistry, University of Wrocław ul. 14 F. Joliot-Curie, 50-383 Wrocław (Poland), Fax: (+48) 71-3282348 http://llg.chem.uni.wroc.pl/
authors.forename: Aneta
authors.initials: A
authors.lastname: Idec
authors.affiliation: Department of Chemistry, University of Wrocław ul. 14 F. Joliot-Curie, 50-383 Wrocław (Poland), Fax: (+48) 71-3282348 http://llg.chem.uni.wroc.pl/
authors.forename: Ludmiła
authors.initials: L
authors.lastname: Szterenberg
authors.affiliation: Department of Chemistry, University of Wrocław ul. 14 F. Joliot-Curie, 50-383 Wrocław (Poland), Fax: (+48) 71-3282348 http://llg.chem.uni.wroc.pl/. lechoslaw.latos-grazynski@chem.uni.wroc.pl.
authors.forename: Lechosław
authors.initials: L
authors.lastname: Latos-Grażyński
keywords: alkenes; carbaporphyrin; contraction; porphyrinoids; rhodium