Telluracarbaporphyrins and a Related Palladium(II) Complex: Evidence for Hypervalent Interactions

Lash, Timothy D.; AbuSalim, Deyaa I.; Ferrence, Gregory M.

doi:10.1021/acs.inorgchem.1c01039

Cited by 11 publications

(22 citation statements)

References 48 publications

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“…Heterocarbaporphyrins possessing NCNX-coordination spheres (X = O, S, Se, Te) combine the features of the trianionic carbaporphyrins with those of the monoanionic chalcogen-based heteroporphyrins and may act as dianionic ligands (examples shown in Scheme ). Derivatives featuring, for instance, isomeric CONN or tris-modified CNTeO cores have also become known . Synthesized along classic [3 + 1]-type pathways using a heterotripyrrane and a carba-building block, , the β-alkyl- , as well as the meso -aryl-derivatives , were reported.…”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

“…Select examples of carbaporphyrins and heteroporphyrins have been known longer and were studied more intensely than most other examples, including their coordination chemistry. Examples include N-confused and N-fused porphyrins, − benzocarbaporphyrins, and their heteroanalogues. ,, They have been thoroughly reviewed in the current literature; consequently, we provide only an abbreviated overview, with reference to the detailed accounts.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the reduction of (hydro)porphyrins may lead to the formation of their leuco -form, the porphyrinogens. , While their free-bases are preferentially in the porphyrinogen tautomeric form (5,10,15,20,22,24-hexahydroporphyrin), their nickel(II) complexes are in the pyrrocorphin form (2,3,7,8,12,13-hexahydroporphyrin) . Tris-modified (or even tetrakis-modified) − PMPs are rare (even including PMPs with pyrrolines as well as nonpyrrolic moieties), and only comparatively little is known about their metal complexes and electronic structures. , …”

Section: Introductionmentioning

confidence: 99%

“…Examples include N-confused and N-fused porphyrins, 58−62 benzocarbaporphyrins, 63 and their heteroanalogues. 10,64,65 They have been thoroughly reviewed in the current literature; consequently, we provide only an abbreviated overview, with reference to the detailed accounts.…”

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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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Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

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“…For example, the telluraporphyrins have proven to be active catalysts in the bromination reactions of 4-pentenoic acid and 1,3,5-trimethoxybenzene, which is ascribed to the ease of oxidation of core tellurium and subsequent stabilization of the telluronium cation by the trans atom . The telluroporphyrinoids are very air-sensitive and have a tendency to extrude tellurium atom from the telluorophene ring of porphyrinoid. , A perusal of the literature reveals that the tellurophene-containing porphyrinoids are relatively less explored as compared to other heteroporphyrinoids, which may be due to a lack of easily accessible stable tellurophene-based precursors and the high reactivity of the telluroporphyrinoids. ,− In particular, there are very few reports available on tellurophene-containing expanded porphyrinoids to understand their physicochemical and coordination properties. − Herein, we report the synthesis of different types of novel tellurophene-containing core-modified homopentaphyrins by a [3 + 2] condensation strategy.…”

Section: Introductionmentioning

confidence: 99%

Tellurophene-Containing Core-Modified Pentaphyrin(2.1.1.1.1)s

et al. 2022

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Various core-modified tellurophene-containing pentaphyrin(2.1.1.1.1)s were synthesized via (3 + 2) condensation of 16-telluratripyrrane with different heterodiols under mild acid catalyzed conditions in 5–12% yields. The formation of pentaphyrin (2.1.1.1.1) with a N2O2Te core was not successful due to its inherent instability. The new pentaphyrins were characterized and studied by HR-MS, 1D and 2D NMR, X-ray crystallography for one of the pentaphyrins, absorption and DFT/TD-DFT techniques. The NMR studies indicated their nonaromatic nature. The X-ray structure obtained for pentaphyrin(2.1.1.1.1) with N4Te core revealed that the macrocycle exists in a highly distorted nonplanar structure. The DFT studies showed that the macrocycles are nonaromatic and exists in highly distorted nonplanar geometry. Furthermore, as the core heterocyclic groups at ethene moiety were changed from pyrrole to furan to thiophene to benzene, the macrocycles tended toward more planar structures. The absorption spectra of pentaphyrins showed one strong sharp band in the region of 450–540 nm along with a broad band in the region of 700–800 nm. The pentaphyrin(2.1.1.1.1) with N4Te core upon protonation showed distinct color change in solution and large bathochromic shifts in absorption bands with an absorption in the NIR region.

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