Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I

Senge, Ma­thias O.

doi:10.1515/znb-1993-0724

Cited by 9 publications

(1 citation statement)

References 12 publications

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“…Structurally, 38 was found to exhibit a structural profile akin to that of 5,15‐dioxoporphyrins. [ 103 ] In 2016 Sugiura's group presented the synthesis of 40 , the 5,10‐analogue of 38 . [ 104 ] The UV/Vis spectrum of the molecule was vastly different, with a bathochromic shift on the second band, up to 694 nm, and hypsochromic of the first, down to 437 nm, along with some IR absorption at 920 nm.…”

Section: Snar Reactions Of Porphyrinsmentioning

confidence: 99%

Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

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Senge

2020

Eur J Org Chem

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The nucleophilic substitution of aromatic moieties (SNAr) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. Currently, several “types” of SNAr reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein, we detail the SNAr reactions of seven types of porphyrinoids with differing number and type of pyrrole units: subporphyrins, norcorroles, corroles, porphyrins, azuliporphyrins, N‐confused porphyrins, and phthalocyanines. For each we analyze the substitution dependent upon: a) the type of nucleophile and b) the site of substitution (α, β, or meso). Along with this we evaluate this route as a synthetic strategy for the generation of unsymmetrical porphyrinoids. Distinct trends can be identified for each type of porphyrinoid discussed, regardless of nucleophile. The use of nucleophilic substitution on porphyrinoids is found to often be a cost‐effective procedure with the ability to yield complex substituent patterns, which can be conducted in non‐anhydrous solvents with easily accessible simple porphyrinoids.

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Section: Snar Reactions Of Porphyrinsmentioning

confidence: 99%

Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

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Senge

2020

Eur J Org Chem

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Synthesis and Characterization of 5,10‐ and 5,15‐Disubstituted Porphodimethenes

et al. 2012

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The four porphodimethene isomers, 5,10‐ and 5,15‐disubstituted, have been synthesized in a one‐pot reaction by the Lindsey protocol. Three of them have been characterized by X‐ray crystallography. Structures show that two of them are 5,15‐porphodimethenes: one is syn‐equatorial, another is anti‐configuration; the third one is 5,10‐porphodimethene. In the 5,10‐porphodimethene, the tripyrrane subunit remains planar conformation. 1H NMR and UV‐vis spectra have also been characterized. Both spectra reveal remarkable difference between 5,10‐ and 5,15‐disubstituted isomers.

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Experimental and Theoretical Characterization of 5,10‐Diminoporphodimethenes: Dearomatized Porphyrinoids from Palladium‐Catalyzed Hydrazinations of 5,10‐Diarylporphyrins

et al. 2014

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A new dearomatized porphyrinoid, 5,10‐diiminoporphodimethene (5,10‐DIPD), has been prepared by palladium‐catalyzed hydrazination of 5,10‐dibromo‐15,20‐bis(3,5‐di‐tert‐butylphenyl)porphyrin and its nickel(II) complex, by using ethyl and 4‐methoxybenzyl carbazates. The oxidative dearomatization of the porphyrin ring occurs in high yield. Further oxidation with 2,3‐dichloro‐5,6‐dicyanobenzoquinone forms the corresponding 5,10‐bis(azocarboxylates), thereby restoring the porphyrin aromaticity. The UV/visible spectra of the NiII DIPDs exhibit remarkable redshifts of the lowest‐energy bands to 780 nm, and differential pulse voltammetry reveals a contracted electrochemical HOMO–LUMO gap of 1.44 V. Density functional theory (DFT) was used to calculate the optimized geometries and frontier molecular orbitals of model 5,10‐DIPD Ni7c and 5,10‐bis(azocarboxylate) Ni8c. The conformations of the carbamate groups and the configurations of the CNZ unit were considered in conjunction with the NOESY spectra, to generate the global minimum geometry and two other structures with slightly higher energies. In the absence of solution data regarding conformations, ten possible local minimum conformations were considered for Ni8c. Partition of the porphyrin macrocycle into tri‐ and monopyrrole fragments in Ni7c and the inclusion of terminal conjugating functional groups generate unique frontier molecular orbital distributions and a HOMO–LUMO transition with a strong element of charge transfer from the monopyrrole ring. Time‐dependent DFT calculations were performed for the three lowest‐energy structures of Ni7c and Ni8c, and weighting according to their energies allowed the prediction of the electronic spectra. The calculations reproduce the lower‐energy regions of the spectra and the overall forms of the spectra with high accuracy, but agreement is not as good in the Soret region below 450 nm.

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Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I

Cited by 9 publications

References 12 publications

Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

Synthesis and Characterization of 5,10‐ and 5,15‐Disubstituted Porphodimethenes

Experimental and Theoretical Characterization of 5,10‐Diminoporphodimethenes: Dearomatized Porphyrinoids from Palladium‐Catalyzed Hydrazinations of 5,10‐Diarylporphyrins

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Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I

Cited by 9 publications

References 12 publications

Nucleophilic Aromatic Substitution (SNAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

Nucleophilic Aromatic Substitution (SNAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

Synthesis and Characterization of 5,10‐ and 5,15‐Disubstituted Porphodimethenes

Experimental and Theoretical Characterization of 5,10‐Diminoporphodimethenes: Dearomatized Porphyrinoids from Palladium‐Catalyzed Hydrazinations of 5,10‐Diarylporphyrins

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Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

Nucleophilic Aromatic Substitution (S_NAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects