Late transition metal complexes of oxypyriporphyrin and the platinum(II) complex of oxybenziporphyrin

Pokharel, Komal; Ferrence, Gregory M.; Lash, Timothy D.

doi:10.1142/s1088424617500535

Cited by 7 publications

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“…Oxybenziporphyrins (e.g., 37 ) are the favored keto tautomers of 2-hydroxybenziporphyrins . The system can act as a trianionic ligand, and examples of silver(III) and gold(III) complexes of oxybenziporphyrins have been reported. − However, oxybenziporphyrin 37 reacted with palladium(II) chloride in the presence of potassium carbonate to give an anionic palladium(II) complex 38 (Scheme ) and a related platinum(II) complex, isolated as a hydroxybenziporphyrin derivative, has also been noted . Interestingly, reaction of 38 with methyl iodide gave a C-alkylation product 39 with strongly diatropic properties (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…53−55 However, oxybenziporphyrin 37 reacted with palladium(II) chloride in the presence of potassium carbonate to give an anionic palladium(II) complex 38 (Scheme 9) 56 and a related platinum(II) complex, isolated as a hydroxybenziporphyrin derivative, has also been noted. 57 Interestingly, reaction of 38 with methyl iodide gave a C-alkylation product 39 with strongly diatropic properties (Scheme 9). 56 The proton NMR spectrum for this species gave four downfield singlets for the meso-protons at 9.20, 9.22, 9.25, and 10.40 ppm, while the internal methyl group gave an upfield 3H singlet at −2.00 ppm.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems

Latham

Lash

2020

J. Org. Chem.

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MacDonald-type "3 + 1" condensations of an N-methyltripyrrane with a series of dialdehydes afforded a matched set of N-methylporphyrins, Nmethylheteroporphyrins, N-methyloxybenziporphyrin, N-methyloxypyriporphyrin, N-methyltropiporphyrin, and a N-methylcarbaporphyrin aldehyde. meso-Unsubstituted heteroporphyrins have been little explored previously, and this strategy was also used to prepare N-unsubstituted 21-oxa-, 21-thia-, and 21-selenaporphyrins. In every case, the N-methylporphyrinoids exhibited weaker, bathochromically shifted UV−Vis absorptions compared to their core unsubstituted congeners. However, proton NMR spectroscopy demonstrated that these derivatives retained strong diamagnetic ring currents and the presence of the internal alkyl substituents had little effect on the global aromatic characteristics. Nevertheless, the UV−Vis spectra of N-methyl-oxybenzi-and N-methyl-oxypyriporphyrins were dramatically altered and gave greatly weakened absorptions. N-Methyl-oxybenzi-and N-methyltropiporphyrins reacted with palladium(II) acetate to give stable palladium(II) complexes, demonstrating that N-alkylation alters the metalation properties for these carbaporphyrinoids. The organometallic derivatives also retained strongly aromatic properties, and the proton NMR spectra showed the N-methyl resonances near −3 ppm. N-Methylcarbaporphyrin-2-carbaldehyde also gave a palladium(II) complex, but this gradually rearranged at higher temperatures to afford a C-methyl complex. The results demonstrate that core alkylation of porphyrinoids greatly alters the reactivity and spectroscopic properties for these systems.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems

Latham

Lash

2020

J. Org. Chem.

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“…Remarkably, the inner carbon of the complex 116Pd is sufficiently nucleophilic to be alkylated, forming the neutral N -methyloxybenziporphyrin palladium complex 116 Me‑I Pd . While conventional metal insertion conditions failed to result in the formation of the targeted platinum(II) complex of oxybenziporphyrins, moderate yields were obtained when oxypyriporphyrin was reacted with platinum(II) chloride in refluxing mixtures of DMF and acetic acid containing potassium acetate …”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

“…Metalation of the diprotic dimethoxybenziporphyrins with nickel(II) and palladium(II) resulted in the formation of 113Ni and 113Pd , respectively . The X-ray structure of 113Ni shows that the macrocycle adopts a saddled geometry with the dimethoxybenzene bent out of plane, generating a distorted square-planar N 3 C-coordination geometry. , …”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

“…While conventional metal insertion conditions failed to result in the formation of the targeted platinum(II) complex of oxybenziporphyrins, moderate yields were obtained when oxypyriporphyrin was reacted with platinum(II) chloride in refluxing mixtures of DMF and acetic acid containing potassium acetate. 435 Core-modified oxybenziporphyrins are oxybenziporphyrins in which at least one pyrrolic nitrogen has been replaced by an O, S, or Se atom (cf. the heteroporphyrins described in Section 2.3).…”

Section: Metallothiaethyneporphyrin Metal Complexesmentioning

confidence: 99%

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Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

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The replacement of one or more pyrrolic building block(s) of a porphyrin by a nonpyrrolic heterocycle leads to the formation of so-called pyrrole-modified porphyrins (PMPs), porphyrinoids of broad structural variability. The wide range of coordination environments (type, number, charge, and architecture of the donor atoms) that the pyrrole-modified frameworks provide to the central metal ions, the frequent presence of donor atoms at their periphery, and their often observed nonplanarity or conformational flexibility distinguish the complexes of the PMPs clearly from those of the traditional square-planar, dianionic, N 4 -coordinating (hydro)porphyrins. Their different coordination properties suggest their utilization in areas beyond which regular metalloporphyrins are suitable. Following a general introduction to the synthetic methodologies available to generate pyrrole-modified porphyrins, their general structure, history, coordination chemistry, and optical properties, this Review highlights the chemical, electronic (optical), and structural differences of specific classes of metalloporphyrinoids containing nonpyrrolic heterocycles. The focus is on macrocycles with similar "tetrapyrrolic" architectures as porphyrins, thusly excluding the majority of expanded porphyrins. We highlight the relevance and application of these metal complexes in biological and technical fields as chemosensors, catalysts, photochemotherapeutics, or imaging agents. This Review provides an introduction to the field of metallo-PMPs as well as a comprehensive snapshot of the current state of the art of their synthesis, structures, and properties. It also aims to provide encouragement for the further study of these intriguing and structurally versatile metalloporphyrinoids.

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Synthesis of meta- and para-benziporphyrinoids and their organometallic complexes

Yadav,

Mangalampalli

2024

Tetrahedron

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Late transition metal complexes of oxypyriporphyrin and the platinum(II) complex of oxybenziporphyrin

Cited by 7 publications

References 38 publications

Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems

Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Synthesis of meta- and para-benziporphyrinoids and their organometallic complexes

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