The Porphyrinogen−Porphodimethene Relationship Leading to Novel Synthetic Methodologies Focused on the Modification and Functionalization of the Porphyrinogen and Porphodimethene Skeletons

The general synthetic methods presented in this paper make available, on a preparative scale, unprecedented porphyrinogen-derived skeletons, including their functionalization at the meso positions. The stepwise dealkylation of meso- octaalkylporphyrinogen R 8 N 4 H 4 [R = Et, 1; R = Bu n, 2 ] was chemically, mechanistically, and structurally followed until the formation of porphomethene and porphodimethene derivatives 5 − 13, obtained with a sequential use of SnCl 4 . In particular, the porphodimethene derivative [(Et 6 N 4 )SnCl 2 ], 9, was reductively transmetalated using Li metal to Et 6 N 4 Li 2, 14, subsequently hydrolyzed to Et 6 N 4 H 2, 15 . The porphodimethene−nickel complex [(Et 6 N 4 )Ni], 16, was used for studying the reactivity and the ligand modification of the porphodimethene skeleton. The reactivity of 16 toward nucleophiles led to otherwise inaccessible meso-substituted-meso-functionalized porphyrinogens [(Et 6 N 4 R 2 )NiLi 2 ], [R = H, 18; R = Bu n, 19; R = CH 2 CN, 20 ], thus exemplifying a general methodology to meso-functionalized porphyrinogens. In addition, when [NMe 2 ] - was used as the nucleophile, 16 was converted into mono- and bis-vinylideneporphyrinogen derivatives [{Et 4 ( CHMe)N 4 }NiLi], 21, and [{Et 5 ( CHMe) 2 N 4 }NiLi 2 ], 22, through the intermediacy of meso -(dimethylamino)-porphyrinogens undergoing an α-H elimination from the meso positions. Such intermediates were isolated and characterized in the stepwise reaction of 14 with LiNMe 2 leading to [{Et 6 (NMe 2 ) 2 N 4 }Li 4 ], 23, and [{Et 5 (NMe 2 )( CHMe)N 4 }Li 4 ], 25 . Both compounds, as a function of the reaction solvent, undergo the thermal elimination of HNMe 2 with the formation of [{Et 4 ( CHMe) 2 N 4 }Li 4 ], 24, which is then protonated to [{Et 4 ( CHMe) 2 N 4 }H 4 ], 27 . Transmetalation from 23 to 24 can be used as the methodology for the synthesis of a remarkable variety of meso-substituted and functionalized porphyrinogen complexes. The deprotonation of 16 is reversible, therefore 22 and 23 can be protonated back to their starting materials. We took advantage of the nucleophilicity of the vinylidene carbon in 21 and 22 for establishing a general synthetic method to produce meso-functionalized porphodimethenes. This approach was exemplified with the alkylation and the benzoylation of 22 and 21 leading to [{Et 4 Pr i 2 N 4 }Ni], 28, [Et 4 {CH(Me)(PhCO)} 2 N 4 Ni], 29, and [Et 5 {CH(Me)(PhCO)}N 4 Ni], 30, respectively. Complex 21 displays a bifunctional behavior, as shown by the formation of 30, whereas in the reaction with LiBu, led to [{Et 5 (Bu n )( CHMe)N 4 }NiLi 2 ], 31 .