π-Complexes of metalloporphyrins as model intermediates in hydrodementallation (HDM) catalysis

Dailey, Karen Koczaja; Rauchfuss, Thomas B.

doi:10.1016/s0277-5387(96)00549-9

Cited by 29 publications

(12 citation statements)

References 53 publications

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“…While studying catalytic hydrodemetalation, Rauchfuss and co-workers realized that the pyrrole rings of the tetrapyrrolic macrocycles could act as h 5 -pyrrolide ligands for p complexes. [137][138][139] Figure 5). The stability of these complexes is related to the electron-donating ability of the porphyrin ring.…”

Section: Other P-complexesmentioning

confidence: 99%

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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: Other P-complexesmentioning

confidence: 99%

“…Porphyrinocenes developed by Rauchfuss. [138,139] Scheme 15. Mercurated and palladated porphyrins used by Smith and co-workers.…”

Section: Ring-metalated Porphyrins As Synthetic Intermediatesmentioning

confidence: 99%

Merging Porphyrins with Organometallics: Synthesis and Applications

2008

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“…The first example of p-bonding involving one of the pyrrole units of a porphyrin was reported by Rauchfuss et al in the middle 1990s. 10,11 ) in dichloromethane affording the bimetallic species 9-11 (Fig. 5).…”

Section: Directly P-metallated Porphyrinsmentioning

confidence: 99%

π-Metal complexes of tetrapyrrolic systems. A novel coordination mode in “porphyrin-like” chemistry

Cuesta

Sessler

2009

Chem. Soc. Rev.

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The coordination chemistry of porphyrins and related tetrapyrrolic ligands has traditionally centered around the ability of these systems to form pyrrole N-ligated complexes via the formation of sigma bonds, either within the N(4) core or displaced above it. In fact, such sigma-complexes are known with almost every metal cation in the periodic table. However, a growing number of pi-complexes derived from tetrapyrrolic ligands have been reported in recent years. The underlying coordination mode, while still novel in the context of "porphyrin-like" chemistry, is already being recognized for the effects it can impart over the reactivity, as well as the spectroscopic, redox, electronic, and optical properties of various oligopyrrolic macrocycles. This critical review summarizes accomplishments made in this fast-emerging field (59 references).

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“…On the other hand, triple-decker π-ruthenium complex of bis-Pd(II) [26]hexaphyrin 3 possesses two ( p -cymene)Ru II fragments sitting on the two Pd II metal centers and the inner pyrrolic β-carbon atoms in a η 6 -coordinated manner on both sides of the hexaphyrin. In the literature, π-metal complexes of porphyrinoids have been limited to those based on porphyrin, porphycene, subphthalocyanine, and subporphyrazine scaffolds [ 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ], and no examples had been reported for expanded porphyrin π-metal complexes before our report [ 8 ]. Interestingly, complexes 1 and 2 showed attenuated macrocyclic paratropic ring currents, probably due to the coordination-induced attenuation of the global conjugation circuit, while complex 3 showed distinct 26π aromaticity.…”

Section: Introductionmentioning

confidence: 99%

Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes

2020

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Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex 4 was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex 3 and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex 6 was obtained upon treatment of bis-Pd(II) [26]hexaphyrin 5 with [RuCl2(p-cymene)]2 under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for 4 and 6 by 1H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity.

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π-Complexes of metalloporphyrins as model intermediates in hydrodementallation (HDM) catalysis

Cited by 29 publications

References 53 publications

Merging Porphyrins with Organometallics: Synthesis and Applications

Merging Porphyrins with Organometallics: Synthesis and Applications

π-Metal complexes of tetrapyrrolic systems. A novel coordination mode in “porphyrin-like” chemistry

Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes

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