Porphyrin ring pdf

The data from the various experiments are depicted in Table S2 and graphically represented in Figure S Table S2: Experimental K values at varying temperatures. Determination of the binding constant for 2-phenylpyrrolidine 5c.

A stock solution [Co TMP ] catalyst 3 2. Under nitrogen the stock solution of the guest 5b was titrated to the host solution 3 at K and the changes in absorption was monitored at nm and nm.

The binding constant for the starting material 4-azidobutyl benzene 5a could not be obtained due to the very low binding constant. A simplified model porphyrin without meso-substituents was used to reduce computation time. Geometry optimizations were carried out with the Turbomole program package[27] coupled to the PQS Baker optimizer[28] via the BOpt package. All minima no imaginary frequencies and transition states one imaginary frequency were characterized by calculating the Hessian matrix.

ZPE and gas-phase thermal corrections entropy and enthalpy, K, 1 bar from these analyses were calculated. The nature of the transition states was confirmed by following the intrinsic reaction coordinate. DFT calculations without dispersion corrections strongly underestimate the metal-ligand interactions, as was clear from a series of test calculations.

This is due to neglected dispersion interactions between the metal binding site of the catalyst and a solvent molecule in solution. However, this approach also leads to an erroneous cancelation of all translational entropy contributions to the computed free energies. This leads to realistic metal-ligand binding entropies comparable to those reported for related systems in toluene. We anticipated that the initial steps of the mechanism might involve coordination of the aliphatic azide 5a to cobalt II , followed by dinitrogen loss to produce a related nitrene-radical intermediate Table S4.

This indeed is a plausible pathway. However, dissociation of amine product 5c from cobalt II species E is endergonic, resulting in product inhibition. This is in agreement with the experimental data, as an amine trapping agent Boc2O is required for catalytic turnover. To further evaluate the effect of product inhibition on the reaction barriers, both unsaturated 5-coordinate cobalt and saturated pathways 6- coordinate cobalt, having pyrrolidine 5c bound trans to the reactive site were considered computationally.

The azide activation barrier for the 5-coordinated analog is about 4 kcal mol-1 higher than with the corresponding 4-coordinated complex A. It is clear from these studies that product adduct E becomes the resting state if the unprotected amine product 5c is not removed from the reaction mixture, while azide adduct B is the resting state if 5c is trapped by an amine scavenger such as Boc2O.

The overall barrier from E to TS1 rate limiting step in absence of Boc2O is much higher than the barrier from B to TS1 rate limiting step in presence of Boc2O and as such, the computations are in good agreement with the experimental observations. Hsu, T. Yang, C. Peng, Polym. Kadish, C. Araullo-McAdams, B. Franzen, J.

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Turner, E. Hiroya, R. Jouka, M. The names of the files indicate the species. Reprints and Permissions. Global aromaticity at the nanoscale. Download citation.

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Subjects Organic chemistry Supramolecular chemistry. Abstract Aromaticity can be defined by the ability of a molecule to sustain a ring current when placed in a magnetic field.

Access through your institution. Buy or subscribe. This is a preview of subscription content. Change institution. Buy article Get time limited or full article access on ReadCube. Data availability All relevant data, including raw computational data from the NICS calculations as well as XYZ coordinates of calculated molecular geometries, are available within the paper and its Supplementary Information files. References 1.

Article Google Scholar 8. Article Google Scholar Article Google Scholar Download references. Peeks Authors Michel Rickhaus View author publications. View author publications. Ethics declarations Competing interests The authors declare no competing interests.

Supplementary information. Supplementary information Details of experimental procedures, computational methods, synthetic schemes, NMR spectra, electrochemical data and results of DFT calculations testing a range of functionals. NICS values 42 data files in comma-separated-values csv format. Rights and permissions Reprints and Permissions. About this article. Cite this article Rickhaus, M. Copy to clipboard. Gonsales Adam S. Fraser Stoddart Nature Chemistry Search Search articles by subject, keyword or author.

Show results from All journals This journal. Close banner Close. Email address Sign up. Synthesis of beta - aryl substituted porphyrins by palladium catalyzed Suzuki cross-coupling reactions. Novel dodecaarylporphyrin: synthesis and dynamic properties. Carborane functionalized pyrroles and porphyrins via the Suzuki cross-coupling reaction. Allenylporphyrins: a new motif on the porphyrin periphery. Facile and efficient synthesis of meso -arylamino- and alkylamino-substituted porphyrins via palladium-catalyzed amination.

Chem [ PubMed ] [ Google Scholar ]. Versatile synthesis of meso -aryloxy- and alkoxy-substituted porphyrins via palladium-catalyzed C-O cross-coupling reactions.

Palladium-catalyzed meso -amination and amidation of porphyrins: marked acceleration with the Ni II central metal ion. Modified porphyrinoids from carbazates and hydrazones and the first crystal structure of a diiminoporphodimethene. General synthesis of meso -amidoporphyrins via palladium-catalyzed amidation.

Palladium-mediated synthesis of novel meso -chiral porphyrins: cobalt-catalyzed cyclopropanation. Synthesis of meso -arylsulfanyl- and alkylsulfanyl-substituted porphyrins via palladium-mediated C-S bond formation.

Structure and optical properties of porphyrin dimers linked by peripherally fused phosphametallacycles. Exploration of the reaction of potassium organotrifluoroborates with porphyrins. Suzuki porphyrins: New synthons for the fabrication of porphyrin-containing su- pramolecular assemblies. Syntheses and 1H NMR spectroscopy of rigid, cofacially aligned, porphyrin-bridge-quinone systems in which the interplanar separations between the porphyrin, aromatic bridge, and quinone are less than the sum of their respective van der Waals radii.

Catalytic O-O activation chemistry mediated by iron hangman porphyrins with a wide range of proton-donating abilities.

Proton-coupled O-O activation on a redox platform bearing a hydrogen-bonding scaffold. Design, synthesis, linear, and nonlinear optical properties of conjugated porphinato zinc II -based donor-acceptor chromophores featuring nitrothiophenyl and nitrooligothiophenyl electron-accepting moieties.

Excited-state energy-transfer dynamics of self-assembled imine-linked porphyrin dyads. Novel zinc porphyrin sensitizers for dye-sensitized solar cells: synthesis and spectral, electrochemical, and photovoltaic properties. Tetrapyrrole derivatives substituted with ferrocenylethynyl moieties. Synthesis and electrochemical studies. Multifunctional bacteriochlorins from selective palladium-coupling reactions.

Syntheses of aryl- and arylethynyl-substituted N-confused porphyrins. An efficient synthetic approach to highly conjugated porphyrin-based assemblies containing a bipyridine moiety. Synthesis and crystal structure of a push-pull quinoidal porphyrin: a nanoporous framework assembled from cyclic trimer aggregates. A concise approach to the synthesis of opp -dibenzoporphyrins through the Heck reaction.

Triphenylene-fused porphyrins. Water-soluble ionic benzoporphyrins. Palladium-catalyzed Kumada Coupling Reaction of bromoporphyrins with silylmethyl Grignard reagents: Preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems.

A: Chem. Electrophilic substitution on porphin. Orientation of electrophilic meso-substitution in metallooctaethylporphyrins. Datta-Gupta, N. The reaction of metalloporphyrins with nitrogen dioxide. Nitrooctaethylporphyrins: synthesis, optical and redox properties. Dihydroporphyrin synthesis: new methodology. Efficient peripheral functionalization of porphyrins. Shimidzu, H. Synthesis of porphyrin-2,3,12, and -2,3,7,8-tetraones: building blocks for the synthesis of extended porphyrin arrays.

Efficient peripheral functionalization of capped porphyrins. Syntheses of chlorins possessing fused nitrogen-containing rings. A new and highly efficient synthesis of hydroxyporphyrins. A general reductive denitration method for regiospecific deuteriation of the porphyrin nucleus: synthesis of [ Reaction of 5-nitrooctaethylporphyrins with nudeophiles. A new method for regiospecific deuteration and reduction of 5,10,15,tetraphenylporphyrins: nucleophilic reaction of borohydride ion with 2-nitro-5,10,15,tetraphenylporphyrins.

A convenient synthesis of 2-Alkyl-5,10,15,tetraphenylporphyrins: reaction of metallonitro-5,10,15,tetraphenylporphyrins with Grignard and organolithium reagents.

Reaction of metallonitro-5,10,15,tetraphenylporphyrins with oxyanions. Temperature-dependent competition between nucleophilic addition and single-electron transfer processes. Solvent-dependent ambident nucleophilicity of phenoxide ion towards nitroporphyrins: synthesis of 2-hydroxyaryl- and 2-aryloxy-5,10,15,tetraphenylporphyrins by displacement of a nitro group.

A convenient synthesis of functionalized tetraphenylchlorins. First syntheses of fused pyrroloporphyrins. Regioselective syntheses and structural characterizations of 2,3-dibromo- and 2,3,7,8,12,hexabromo-5,10,15,tetraphenylporphyrins.

Polyformylation of copper II porphyrins. Polyformylation of copper II complexes of octa-alkyl porphyrins. Electrophilic substitution reactions of derivatives of deuteroporphyrin-IX: deuteriation and Vilsmeier formylation. Efficient new syntheses of benzochlorins, benzoisobacteriochlorins and benzobacteriochlorins. Vilsmeier reactions of porphyrins and chlorins with 3- dimethylamino acrolein. New syntheses of benzochlorins, benzoisobacteriochlorins and dibenzobacteriochlorins and reductive coupling of porphyrins and chlorins using low-valent titanium complexes.

An improved method for the preparation of formyldeuteroporphyrins. Synthesis of biologically relevant porphyrins. The dithianyl group as a synthon in porphyrin chemistry: condensation reactions and preparation of formylporphyrins under basic conditions.

Exploration of meso-substituted formylporphyrins and their Grignard and Wittig reactions. One-pot synthesis of meso -formylporphyrins by SNAr reaction of 5,disubstituted porphyrins with 2-pyridyldimethylsilyl methyllithium.

Chemistry of pyrrolic compounds. Some aspects of the mass spectra and chemistry of meso-substituted porphyrins. Some reactions of meso - formyloctaethylporhyrin. A facile method for the preparation of porphyrins with exocyclic double bonds. A simple synthesis of functionalized rac -chlorins via allylboration of porphyrin aldehydes. Preparation of bacteriopetroporphyrins by partial synthesis from the Chlorobium chlorophylls.

Energy Fuels. General synthesis of hydrocarbon-soluble porphyrins. Recent studies on the Chloro- bium chlorophylls bacteriochlorophylls-c Int. Meso methine functionalization of octaalkylporphyrins. The synthesis of butadiene-bridged porphyrindimers and styryl porphyrins using a porphyrin-derived Wittig reagent.

Functionalizing porphyrins via Wittig reactions: a building block approach. Structurally homologous beta- and meso-amidinium porphyrins. Novel boronated derivatives of 5,10,15,tetraphenylporphyrin: Synthesis and toxicity for drug-resistant tumor cells.

Synthesis and properties of cis-1,2-bis octaethylporphyrinyl ethylene. Synthesis and properties of ethane-bis porphyrins Khim. Synthesis and properties of etheno-bridged porphyrin trimers. Synthesis of meso -monosubstituted ethane- and trans - ethylenebis porphyrins Tetrahedron Lett. Reductive dimerization of the cuprous complex of 2-formyl-5,10,15,tetraphenylporphyrin.

Nauk USSR. Models for the photosynthetic reaction center - synthesis and structure of 1,2-cis- and -trans-ethene and skewed 1,1-carbinol bridged porphyrin dimers. Synthesis and characterization of bis chlorin s from the McMurry reaction of formylchlorins. Direct arylation of meso -formyl porphyrin. Porphyrines synthetiques porteuses dechaines laterales peptidiques.

The preparation of porphyrin S dehydroco-prophyrin and harderoporphyrin from protoporphyrin-IX. Porphyrin dimers linked by conjugated butadiynes. A conformationally constrained conjugated porphyrindimer. Improved methods for the synthesis of porphyrin alcohols and aldehydes from protoporphyrin IX dimethyl ester and their further modification. Making conjugated connections to porphyrins: a comparison of alkyne, alkene, imine and azo links. Synthesis of fluorinated analogs of hematoporphyrin II.

Selective acetylation of porphyrins possessing a free pyrrolic position as a tool for petroporphyrin analysis. A reinvestigation. Partial syntheses of the isomerically pure magnesium II protoporphyrin IX mono-methyl esters and their identification. Enantioselective synthesis of hematoporphyrin stereoisomers. Tetrahedron: Asymm. A simple, chirogenic, enantioselective synthesis of chlorins and isobacteriochlorins. Synthesis of enantiomerically pure hydroxuyeth- ylporphyrins and their transformation into optically active chlorin derivatives.

Part 4. Total synthesis of cyclopentenoporphyrins of sedimentary origin: deoxophylloerythroetioporphyrin, chlorophyll c fossils and related compounds. An unexpected Wittig reaction of dimethyl 3,3'- 3-formyl-2,7,12,tetramethylH, 23H-porphyrin,diyl -dipropionate. Bile pigment studies. Ring cleavage of meso-tetraphenylporphyrin. Synthesis of meso-pyridinium porphyrin salts.

Metalloporphyrins in polymeric matrices, micelles and vesicles, V. Synthesis and reactivity of meso - 3-carbamoylpyridinio -porphyrins. Ion radicals. Reactions of zinc tetraphenylporphyrin cation radical perchlorate with nucleophiles. Novel meso-substitution reactions of metalloporphyrins. One-pot electrochemical generation of a porphyrin dimer with a bis diphenylphosphonium acetylene bridge.

Electrosynthesis and characterization of symmetrical and unsymmetrical linear porphyrin dimers and their precursor monomers. An electrosynthetic path toward pentaporphyrins.

Meso - meso linked diporphyrins from 5,10,trisubstituted porphyrins. Facile regioselective meso -iodination of porphyrins. Transfer of oxygen from percarboxylic acids and alkyl hydroperoxides to meso -tetraphenylporphinato cobalt III chloride. Inorg, Chem. Stirring the porphyrin alphabet soup - functionalization reactions for porphyrins. Nucleophilic substitution as a tool for the synthesis of unsymmetrical porphyrins.

Synthesis of directly meso-meso linked bisporphyrins using organolithium reagents. Regioselective reaction of 5,disubstituted porphyrins with organolithium reagents - synthetic access to 5,10,trisubstituted porphyrins and directly meso-meso-linked bisporphyrins. An efficient synthesis of highly functionalized asymmetric porphyrins with organolithium reagents.

Mechanistic studies on the nucleophilic reaction of porphyrins with organolithium reagents. New routes from porphyrins to stable phlorins. Meso -alkylation and reduction of meso -tetraphenyl- and octaalkylporphyrins. Direct meso -alkylation of meso-formylporphyrins using Grignard reagents. Direct hydroxylation at the meso position of gold III tetraphenylporphyrin by nucleophilic addition: novel hydroxyphlorin derivatives. Syntheses and magnetic properties of aryliron III complexes of octaethylporphyrins.

Reversible cobalt-nitrogen alkyl and acyl group migration in cobalt porphyrins. N -Substituted porphyrin formation from carbene iron-porphyrin complexes: a possible pathway for cytochrome P heme destruction.

Hemoprotein destruction. Iron-nitrogen shift of a phenyl group in a porphyrin complex. Acid-catalysed intramolecular cobalt to nitrogen aryl migration and intramolecular reverse reaction in cobalt porphyrins.

Synthesis of N -phenylporphyrins. Organometallic aspects of cytochrome-p metabolism. Generation of a stable 8-bonded Fe IV porphyrin. Oxophlorin oxyporphyrin synthesis. Synthesis of oxophlorins oxyporphyrins from zinc and magnesium porphyrins. Synthesis of mesoporphyrindiones. Part VII. Benzoyloxylation of phenylpyrroles and of octaethylporphyrin. Synthetic and biosynthetic studies of porphyrins. The synthesis of meso oxygenated protoporphyrins.

A stable octaethyloxophlorin radical. Second generation tumour photosensitisers: the synthesis of octa-alkyl chlorins and bacteriochlorins with graded amphiphilic character. Second generation tumour photosensitisers: the synthesis and biological activity of octaalkyl chlorins and bacteriochlorins with graded amphiphilic character.

C-Hydroxy- and C-methylchlorins. A convenient route to heme d and bonellin model compounds. Migratory aptitudes in pinacol rearrangement of vic- dihydroxychlorins. MO study of the possibility of a concerted mechanism in the pinacol rearrangement.

Syntheses of stable bacteriochlorophyll-a derivatives as potential photosensitizers for photodynamic therapy. Pinacol-pinacolone rearrangements in vic-dihydroxychlorins and bacteriochlorins: effect of substituents at the peripheral positions. A novel method of functionalizing the ethyl chain of octaethylporphyrin. Differentiation of bacteriochlorin and isobacteriochlorin formation by metallation.

High yield synthesis of porphyrindiones via OsO4 oxidation. Substituent effects in tetrapyrrole subunit reactivity and pinacolpinacolone rearrangements: vic -dihydroxychlorins and vic -dihydroxybacterio-chlorins. Syntheses of new bacteriochlorins and their antitumor activity.

Synthesis, photophysical properties. Thiophene-appended porphyrin systems. A rigid chlorin-naphthalene diimide conjugate. A possible new noncovalent electron transfer model system. Fused porphyrin-imidazole systems: new building blocks for synthesis of porphyrin arrays.

Oxidative cleavage of the haem system.