meso-aryl expanded porphyrins: synthesis, structures, and coordination chemistry

meso-aryl expanded porphyrins, that can be regarded as real homologues of meso-tetraaryl porphyrins, were prepared by our synthetic protocol under the modified Rothemund-Lindsey conditions. This new class of molecules exhibits interesting spectral, electrochemical, and coordination properties. These promising features are emphasized, with a particular attention on the annulenic properties.

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Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered

Molecules ◽

10.3390/molecules26040981 ◽

2021 ◽

Vol 26 (4) ◽

pp. 981

Author(s):

Mason D. Hart ◽

John J. Meyers ◽

Zachary A. Wood ◽

Toshinori Nakakita ◽

Jason C. Applegate ◽

...

Keyword(s):

Charge Transfer ◽

Coordination Chemistry ◽

Single Crystal ◽

13C Nmr ◽

Quantitative Assessment ◽

X Ray ◽

New Class ◽

Linear Relationships ◽

Ligand Charge Transfer ◽

Donor Characteristics

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3.

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Coordination chemistry of expanded porphyrins

Coordination Chemistry Reviews ◽

10.1016/j.ccr.2019.213063 ◽

2019 ◽

Vol 401 ◽

pp. 213063 ◽

Cited By ~ 7

Author(s):

A. Alka ◽

Vijayendra S. Shetti ◽

Mangalampalli Ravikanth

Keyword(s):

Coordination Chemistry ◽

Expanded Porphyrins

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ChemInform Abstract: meso-Phenyl Substituted Porphocyanines: A New Class of Functionalized Expanded Porphyrins.

ChemInform ◽

10.1002/chin.199450167 ◽

2010 ◽

Vol 25 (50) ◽

pp. no-no

Author(s):

R. W. BOYLE ◽

L. Y. XIE ◽

D. DOLPHIN

Keyword(s):

New Class ◽

Expanded Porphyrins

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ChemInform Abstract: Synthesis and Coordination Chemistry of a New Class of Binucleating Ligands: Pyridyl-Substituted Diphosphines.

ChemInform ◽

10.1002/chin.199031221 ◽

1990 ◽

Vol 21 (31) ◽

Author(s):

P. H. M. BUDZELAAR ◽

J. H. G. FRIJNS ◽

A. G. ORPEN

Keyword(s):

Coordination Chemistry ◽

New Class ◽

Binucleating Ligands

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Synthesis, coordination chemistry, and physico-chemical properties of the 2-chloroethoxy-iron(III)(ethylthio) porphyrazine

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424613500685 ◽

2013 ◽

Vol 17 (08n09) ◽

pp. 870-880 ◽

Cited By ~ 1

Author(s):

Daniela Pietrangeli ◽

Gaetano Garramone ◽

Maria Rachele Guascito ◽

Antonietta Pepe ◽

Angela Rosa ◽

...

Keyword(s):

Coordination Chemistry ◽

Good Yield ◽

Chemical Properties ◽

Coordination Properties ◽

Physico Chemical ◽

Porphyrin Analogs

Reaction of octakis(ethylthio)porphyrazine ( H 2 OESPz ) with FeBr 2 in ClCH 2 CH 2 OH at 135 °C affords the 2-chloroethoxy-iron(III)-(ethylthio)porphyrazine, ( ClCH 2 CH 2 O ) Fe III OESPz , ( LFe III OESPz ) in good yield. The spectroscopic, redox, and coordination properties of the complex and its μ-oxo dimer derivative, [ Fe III OESPz ]2 O , are investigated and compared to those of the iron(III)porphyrin analogs.

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Benzene- and pyridine-incorporated octaphyrins with different coordination modes toward two PdII centers

Nature Communications ◽

10.1038/s41467-020-20072-9 ◽

2020 ◽

Vol 11 (1) ◽

Author(s):

Le Liu ◽

Zhiwen Hu ◽

Fenni Zhang ◽

Yang Liu ◽

Ling Xu ◽

...

Keyword(s):

Trifluoroacetic Acid ◽

Coordination Modes ◽

Coordination Properties ◽

Subsequent Oxidation ◽

Expanded Porphyrins

AbstractExpanded porphyrins have received considerable attention due to their unique optical, electrochemical and coordination properties. Here, we report benzene- and pyridine-incorporated octaphyrins(1.1.0.0.1.1.0.0), which are synthesized through Suzuki-Miyaura coupling of α,α′-diboryltripyrrane with m-dibromobenzene and 2,6-dibromopyridine, respectively, and subsequent oxidation with 2,3-dicyano-5,6-dichlorobenzoquinone. Both octaphyrins are nonaromatic and take on dumbbell structures. Upon treatment with Pd(OOCCH3)2, the benzene-incorporated one gives a Ci symmetric NNNC coordinated bis-PdII complex but the pyridine incorporated one gives Ci and Cs symmetric NNNC coordinated bis-PdII complexes along with an NNNN coordinated bis-PdII complex bearing a transannular C–C bond between the pyrrole α-positions. In addition, these two pyridine-containing NNNC PdII complexes undergo trifluoroacetic acid-induced clean interconversion.

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