C-H and C-M activation, aromaticity tuning, and Co···Ru interactions confined in the azuliporphyrin framework.

Abstract

Taking advantage of specific properties of azuliporphyrin and reactivity of cobalt(II), activation of azulene C(sp²)-H occurred and organometallic complexes with Co-C bonding were formed. The system allowed for macrocyclic aromaticity tuning through metal coordination and oxidation. Due to Co(II)-C and parallel tested Cu(II)-C reactivity and the affinity of metal centers to dioxygen, oxygen atom insertion to the M-C bond was investigated. Insertion starts with an oxygen molecule coordination and leads to monomeric and dimeric complexes of specific electronic structure. Formation of unique paramagnetic σ/π-hybrid bimetallic complexes formation enabled spectroscopic and theoretical investigations of peculiar Co(II)∙∙∙Ru(0) interactions.