Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

Abstract

The incorporation of ap henanthrene moiety into ap orphyrin framework results in the formation of ah ybrid macrocycle-phenanthriporphyrin-merging the structural features of polycyclic aromatic hydrocarbons and porphyrins. An antiaromatic aceneporphyrinoid, adopting the trianionic {CCNN} core,i ss uitable for the incorporation of ap hosphorus(V) center to form ah ypervalent organophosphorus(V) derivative.

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

“…In the representative case of compound 3-S the degree of out-of-plane distortion is illustrated by the value of the dihedral angle between the phenanthrene moiety and the four meso-carbona toms plane (C 4 plane),w hich equals to 63.74(7)8. Twopyrrole and thiophene rings intersect the C 4 plane with dihedral angles equal to 41.49 (11), 52.67(10), and 13.55(7)8,r espectively.A na nalysiso ft he bond lengths in the phenanthrenylene moiety (Tables S1, S3, and S5 in the Supporting Information) reveals that it preserves the natureo f9 ,10-dihydroxyphenanthrene. [32] The bond lengths C(26)ÀC(1) and C(10)ÀC(11) of 1.482(4) and 1.483(4) , respectively,a re very similar to the C meso ÀC ipso distances of 1.487(4)-1.489 (3) .…”

“…In contrast to the phenanthrisapphyrinst he incorporation of ap henanthrene moiety into ap orphyrin framework resulted in the formation of evidently antiaromatic p system of phenanthriporphyrin where the NICS value of the central 15-membered ring equals 12.1 ppm. [11] Conclusion Motivated by the remarkable antiaromaticity and interesting coordination behavior of recently described phenanthriporphyrin [11] we designed and synthesized ag roup of new aceneporphyrinoids-32-hetero-5,6-dimethoxyphenanthrisapphyrins. Due to geometrical constraints those macrocycles present only ar esidual macrocyclic p conjugation,w hich is preserved after protonation.…”

“…[7][8][9][10] Recently,w edemonstrated that phenanthriporphyrin-an aceneporphyrinoid linking structuralf eatures of phenanthrene and porphyrin-acts as ad istinctively antiaromatic ligand for hypervalent phosphorus(V) producing an organophosphorous(V) derivative. [11] Although the scope of carbaporphyrinoids is constantly extending, [12][13][14][15][16] the number of expanded porphyrins containing carbocyclic moieties is still limited in comparison with their smaller counterparts. Those systemsa re to date represented by azulisapphyrin, [17,18] benzocarbasapphyrin, [17,18] and dibenzoamethyrin, [19] carbasapphyr-in, [20] N-confused heterosapphyrins, [21] doubly N-confused sapphyrin derivatives, [22] expanded benziporphyrinoids, [23][24][25][26][27][28][29] and macrocycles with incorporated triphenylene motifs.…”

“…[30] In this contribution we presentt he synthesis and properties of expandeda ceneporphyrinoids-32-hetero-5,6-dimethoxyphenanthrisapphyrinsa nd 32-thia-5,6-dioxophenanthrisapphyrin. Those macrocycles are structurally relatedtophenanthriporphyrin [11] or tetraarylsapphyrins [31] and might be classified as dicarbasapphyrins (Scheme 1). Actually,p henanthrisapphyrin can be formally derived from sapphyrin by the subsequent replacement of the bipyrrole unit with biphenyl and incorporationo f at wo-carbon bridge linking the phenylene rings of hypothetical biphenylsapphyrin.…”

“…Actually,p henanthrisapphyrin can be formally derived from sapphyrin by the subsequent replacement of the bipyrrole unit with biphenyl and incorporationo f at wo-carbon bridge linking the phenylene rings of hypothetical biphenylsapphyrin. Following this naming system,p henanthriporphyrin [11] might also be considered as phenanthricorrole.…”