2021
DOI: 10.1039/d1cc04870h
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Expanding manganese(iv) aqueous chemistry: unusually stable water-soluble hexahydrazide clathrochelate complexes

Abstract: Mn cage complexes are rare, and the ones successfully isolated in the solid state are not stable in water and organic solvents. Herein, we present the first report of mononuclear...

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Cited by 10 publications
(16 citation statements)
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“…Only six complex types are reported so far with a [MnN 6 ] coordination sphere (Chart ). While some of the manganese­(II,III,IV) complexes have been structurally characterized, e.g., A 3+/2+ , B 2+ , or D (Chart ), no complete series of manganese­(II,III,IV) complexes with a [MnN 6 ] coordination is available so far.…”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…Only six complex types are reported so far with a [MnN 6 ] coordination sphere (Chart ). While some of the manganese­(II,III,IV) complexes have been structurally characterized, e.g., A 3+/2+ , B 2+ , or D (Chart ), no complete series of manganese­(II,III,IV) complexes with a [MnN 6 ] coordination is available so far.…”
Section: Introductionmentioning
confidence: 99%
“…Mn IV complexes should be strong oxidants, but the oxidative power is often damped by strong σ/π donors with E (Mn IV/III ) potentials of [MnN 6 ] complexes ranging from −1.48 to +1.69 V vs ferrocene (Chart ). The highest potentials are achieved by pyridine and pyrazol donors, while strong donors such as guanidines or carbenes and anionic donors such as guanidinates, hydrazides, amides, or azides lower the potential appreciably , (Chart ). Six carbene donors or four carbene donors with two amides furnish E (Mn IV/III ) potentials as low as −0.71 and −0.55 V, respectively. , …”
Section: Introductionmentioning
confidence: 99%
“…This can be achieved by incorporating one or more negatively charged donor atoms to the ligand, which may be viewed as an alternative to the carboxylate ligands and μ-oxo bridges of the Mn 4 CaO 5 cluster . Notable examples of strong σ-donors employed to stabilize M IV and even M V species are carboxamido, hydrazide, phenolate, and carboxylate groups. Importantly, the candidate ligand system would also need to support the binding of one substrate water molecule, as well as stepwise proton release from it, for example, via providing a hydrogen bonding partner .…”
Section: Discussionmentioning
confidence: 99%
“…Cage metal complexes with metal ion(s) encapsulated in a three-dimensional cavity of macropolycyclic ligands (clathrochelates 1 ) are known to be chemically robust coordination compounds possessing unusual chemical, optical, magnetic and redox properties. 1,2 In particular, clathrochelate d -metal( ii ) tris-α-dioximates with apical redox-active mono- and di-thiophene substituents (Chart 1, a ) are reported 3 to undergo electropolymerization, affording the corresponding metal-containing conducting polymers 3 a , b and highly active electrocatalytic systems for hydrogen production from H + ions. 1 b ,3 c…”
Section: Introductionmentioning
confidence: 99%