A new type of chiral porphyrin: Organopalladium porphyrins with chiral chelating diphosphine ligands

Hodgson, Margaret; Borovkov, Victor; Inoue, Yoshihisa; Arnold, Dennis P.

doi:10.1016/j.jorganchem.2005.10.014

Cited by 18 publications

(8 citation statements)

References 40 publications

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“…A meso-iodinated porphyrin was used, because reactions with the meso bromo analogues failed. Later it was realized that these "normal" chelating ligands, which do not have a substantial effect on the porphyrin, can be replaced by chiral, bidentate ligands to give chiral complexes 108 Ni-110 Ni, [162] which could lead to interesting catalytic applications.…”

Section: Methodsmentioning

confidence: 99%

Merging Porphyrins with Organometallics: Synthesis and Applications

2008

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The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or β position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal–carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.

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Section: Methodsmentioning

confidence: 99%

Merging Porphyrins with Organometallics: Synthesis and Applications

2008

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“…Incorporating chirality into organic chromophores could potentially be of interest for many fields of research and a wide variety of applications, either in their monomeric form or as supramolecular aggregates . To this date, various types of chiral chromophores have been studied, including PBIs (perylene bisimides), , BODIPYs (boron-dipyrrins), − porphyrins, − phthalocyanines, , helicenes, − merocyanines, and cyanines . Besides applications in biochemistry and pharmacology, such as in second-harmonic microscopy or as colorimetric molecular sensors, chiral chromophores have been utilized as catalysts in photochemical reactions, as chiroptical sensors, , in organic light-emitting diodes emitting circular polarized light (CP-OLEDs), , in solar cells, as optical molecular switches, , and in photochemical cells used for water splitting …”

Section: Introductionmentioning

confidence: 99%

Chiroptical Properties of Indolenine Squaraines with a Stereogenic Center at Close Proximity

et al. 2020

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A series of four indolenine squaraines bearing a chiral center at the 3-position of the indolenine moiety, with either an n-propyl or a phenyl group alongside a methyl group, were synthesized and obtained in a high purity of ≥98% for the desired stereoisomer. The indolenine precursors with a phenyl group attached at the chiral center were asymmetrically synthesized using a pericyclic-reaction cascade and obtained in a high ee of 98%, whereas the ones with an n-propyl group were prepared by kinetic resolution through asymmetric hydrogenation, resulting in an ee of up to 98%. X-ray crystallography revealed a slightly twisted geometry for the phenyl-substituted cisoid squaraine derivative, whereas the n-propyl-substituted derivative possessed the expected planar geometry. Variation of the substitution also influenced the optical properties, where the introduction of phenyl groups caused a progressive red-shift and reduction in squared transition moments, as well as reduced fluorescence quantum yields, Stokes shifts, and fluorescence lifetimes. All of the investigated compounds exhibited strong ECD signals, with Δε values of up to 24 M −1 cm −1 for the HOMO−LUMO transition. DFT calculations indicated that this was due to both large electric and magnetic transition moments, although the two vectors were mutually almost orthogonal.

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“…These meso -metalated species are important intermediates in palladium-catalyzed cross-coupling reactions. When chiral diphosphine ligands such as BINAP were used, chiral porphyrins were obtained . The induced asymmetry in the porphyrin was detected by 1 H NMR and CD spectroscopy.…”

Section: Reactions Of Halogenated and Metalated Porphyrinsmentioning

confidence: 99%

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies

2016

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This review focuses on the postfunctionalization of porphyrins and related compounds through catalytic and stoichiometric organometallic methodologies. The employment of organometallic reactions has become common in porphyrin synthesis. Palladium-catalyzed cross-coupling reactions are now standard techniques for constructing carbon-carbon bonds in porphyrin synthesis. In addition, iridium- or palladium-catalyzed direct C-H functionalization of porphyrins is emerging as an efficient way to install various substituents onto porphyrins. Furthermore, the copper-mediated Huisgen cycloaddition reaction has become a frequent strategy to incorporate porphyrin units into functional molecules. The use of these organometallic techniques, along with the traditional porphyrin synthesis, now allows chemists to construct a wide range of highly elaborated and complex porphyrin architectures.

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A new type of chiral porphyrin: Organopalladium porphyrins with chiral chelating diphosphine ligands

Cited by 18 publications

References 40 publications

Merging Porphyrins with Organometallics: Synthesis and Applications

Merging Porphyrins with Organometallics: Synthesis and Applications

Chiroptical Properties of Indolenine Squaraines with a Stereogenic Center at Close Proximity

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies

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