Optimization of the Efficiency of Oxidation Catalysts Based on Iron Bispidine Complexes

Comba, Peter; Wadepohl, Hubert; Wiesner, Sebastian

doi:10.1002/ejic.201100212

Cited by 12 publications

(10 citation statements)

References 45 publications

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“…1 with one monodentate ligand trans to N7are known. 25 That is, the coordination geometry around Cu II is comparable to that observed with L 1 (see Table 1). 4,26,27 However, the dangling pyridine donor py4 of L and L OH clearly points in the direction of the Cu II center with a Cu⋯N distance of 3.89 Å and 3.85 Å (L and L OH , respectively), which is an important difference to the structure of the Fe II complex with L 3 .…”

Section: Transition Metal Coordination Chemistrysupporting

confidence: 60%

Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand

2015

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Reported is the new bispidine-derived hexadentate ligand (L = 3-(2-methylpyridyl)-7-(bis-2-methylpyridyl)-3,7-diazabicyclo[3.3.1]nonane) with two tertiary amine and four pyridine donor groups. This ligand can form heterodinuclear and mononuclear complexes and, in the mononuclear compounds discussed here, the ligand may coordinate as a pentadentate ligand, with one of the bispyridinemethane-based pyridine groups un- or semi-coordinated, or as a hexadentate ligand, leading to a pentagonal pyramidal coordination geometry or, with an additional monodentate ligand, to a heptacoordinate pentagonal bipyramidal structure. The solution and solid state data presented here indicate that, with the relatively small Cu(II) and high-spin Fe(II) ions the fourth pyridine group is only semi-coordinated for steric reasons and, with the larger high-spin Mn(II) ion genuine heptacoordination is observed but with a relatively large distortion in the pentagonal equatorial plane.

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Section: Transition Metal Coordination Chemistrysupporting

confidence: 60%

Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand

2015

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“…[102,103] Several other comparative investigations between tetradentate and pentadentate bispidine ligated metal-oxo complexes were also conducted. [104][105][106][107] A comparative olefin epoxidation reaction was also studied between iron(IV)-oxo and ruthenium(IV)-oxo complexes of bispidine. [108] Similar trend between acetonitrile and acetone was observed in the cyclohexane oxidation reaction between iron(IV)-oxo complexes of L1, L2 and L3.…”

Section: Tetradentate Vs Pentadentate Systemsmentioning

confidence: 99%

“…The second‐order rate constant obtained for sulfoxidation of thioanisole by [Fe IV (O)(L3)] 2+ was reported to be 67 M −1 s −1 which is a significantly faster reaction compared to the other iron(IV)‐oxo complexes of fellow biomimetic models [102,103] . Several other comparative investigations between tetradentate and pentadentate bispidine ligated metal‐oxo complexes were also conducted [104–107] . A comparative olefin epoxidation reaction was also studied between iron(IV)‐oxo and ruthenium(IV)‐oxo complexes of bispidine [108] …”

Section: Bispidine Containing Metal‐oxo Speciesmentioning

confidence: 99%

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

Mukherjee

Sastri

2020

Israel Journal of Chemistry

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Ligand framework in a metal complex has a pivotal role to play in orchestrating the spectroscopic and reactivity parameters. High-valent non-heme metal intermediates are known to be crucial species in the catalytic cycles of several metalloenzymes. Among the plethora of a variety of ligand frameworks employed in bioinorganic chemistry, the bispidine molecular scaffold is unique and privileged. In this review, we intend to discuss the overwhelming effects of the bispidine ligand scaffold in tuning the spectroscopic signatures and reactivity parameters of non-heme metal intermediates. The basic skeleton constituting a fused and rigid bicyclic diamine framework with its tentacles tethered to C2, C4, N3 and N7 provides tuneable features to both the primary and secondary coordination spheres. Therefore, the bispidine framework offers a handle to optimize the balance of rigidity and flexibility in a coordination molecule which is thereby important in understanding the rich but surprising results in the reactivity of metal intermediates contained in these scaffolds. Herein, we summarize the significant developments in different types of oxidation reactions of reactive metal intermediates stabilized in bispidine ligands and noted their mechanistic details.

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“…Chair-boat conformations are obtained when a large substituent (such as 2-benzylpyridyl) is introduced at N7 (Figure 4b). 13 However, coordination of the nitrogen atoms N7 and of the pyridyl group drives the formation of a complex with a chairchair conformation. More recently, another structure showing the chair-boat isomer was obtained with a dibromopyridine substituted bispidone.…”

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confidence: 99%

2,4-Substituted bispidines as rigid hosts for versatile applications: from κ-opioid receptor to metal coordination

Nonat

Roux

et al. 2019

Dalton Trans.

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Optimization of the Efficiency of Oxidation Catalysts Based on Iron Bispidine Complexes

Abstract: High-valent bispidine iron-oxo complexes are among the most efficient nonheme iron oxidation catalysts. Here, we report the synthesis and structural analysis of two derivatives of the known pentadentate bispidine ligand

Cited by 12 publications

References 45 publications

Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand

Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

2,4-Substituted bispidines as rigid hosts for versatile applications: from κ-opioid receptor to metal coordination

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