Sepulchrate: a macrobicyclic nitrogen cage for metal ions

Creaser, I. I.; Harrowfield, J. M.; Herlt, Anthony J.; Sargeson, Alan M.; Springborg, J.; Geue, Rodney J.; Snow, MR

doi:10.1021/ja00451a062

Cited by 192 publications

(92 citation statements)

References 2 publications

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“…It is known that in most systems the contributions arising from Franck-Condon parameters outweigh any spin changes. Also significant differences (32) in rates have been identified in the exchange reactions of CO(NH,)~~'/' ' and C o (~e~u l c h r a t e )~+ / ' ' .…”

Section: Discussionmentioning

confidence: 98%

Electron transfer reactions of nickel complexes of 1,4,7-triazacyclodecane

Fairbank¹,

McAuley²,

Norman³

et al. 1985

Can. J. Chem.

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The preparation of [Ni(1,4,7-triazacyciodecane)2]3+, (Ni(10-aneN3)23+) is described. The existing procedure has been modified leading to good yields of the ligand trihydrochloride. The nickel(II) analogue (reported previously) is oxidised in a facile manner, either by Co3+aq in acidic aqueous media or by NO+ in CH3CN. Since the octahedral NiN6, chromophore is retained upon electron transfer, outer sphere reactions both of the Ni(II) and Ni(III) species have been studied. Rates of oxidation by various nickel(III) macrocycles have been measured and details are provided. Electrochemical oxidation of the Ni(II) complex is consistent with E0(Ni(10-aneN3)23+/2+) = 0.997 V (vs. NHE). The data have been used in a Marcus correlation, leading to the self-exchange rate k11 for the couple (Ni(10-aneN3)23+/2+) = (2 ± 1) × 104 M−1 s−1. This value is compared with other data derived using octahedral Ni(II)/Ni(III) centres. The oxidation of the Ni(II) complex by Co(III)aq has been studied in both protonated and deuterated media. There is no evidence for any proton transfer (from the N—H) being coupled to the electron transfer step. The observed rate constant for the reaction of Co3+ with Ni(II)(10-aneN3)22+ (550 M−1 s−1) may be compared with the calculated outer sphere rate (270 M−1 s−1). An estimate of k11 (CoOH2+/+) ~ 3 M−1 s−1 for the CoOH2+/+ exchange is discussed.

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Section: Discussionmentioning

confidence: 98%

Electron transfer reactions of nickel complexes of 1,4,7-triazacyclodecane

Fairbank¹,

McAuley²,

Norman³

et al. 1985

Can. J. Chem.

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“…The force field parameters for bond lengths and bond angles of the Co(II)Sep model were adapted from Dehayes et al 36 and they are reported in 39 observed low and high spin state, respectively. Atomic partial charges were derived using the ChelpG scheme 40 with dipole moment constraint, and they are reported in Table S2 of SI.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Verma

Schwaneberg

Holtmann

et al. 2015

J. Chem. Theory Comput.

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One of the major limitations to exploit enzymes in industrial processes is their dependence on expensive reduction equivalents like NADPH to drive their catalytic cycle. Soluble electron transfer (ET) mediators like Cobalt(II)Sepulchrate have been proposed as a cost-effective alternative to shuttle electrons between an inexpensive electron source and enzyme redox center.The interactions of these molecules with enzymes are not elucidated at molecular level yet.

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“…9,10,14, 26 The imine cage complex [Co(Me 6 docosadieneN 4 S 2 )] 3ϩ (5) was synthesized from a metal template strategy using 1 with paraformaldehyde in the presence of isobutyraldehyde and base. The imine complex proved difficult to reduce cleanly to the saturated analogue using previously described methodologies.…”

Section: 1014mentioning

confidence: 99%

Embracing ligands. A synthetic strategy towards new nitrogen–thioether multidentate ligands and characterization of the cobalt(iii) complexes

2003

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The synthesis of the hexadentate ligand 2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (EtN 4 S 2 amp) is reported. The ligand is of a type in which bifurcations of the chain occur at atoms other than donor atoms. The cobalt() complex [Co(EtN 4 S 2 amp)] 3ϩ (1) was isolated and characterized. The synthetic methodology also results in a number of by-products, notably 2,9,9-tris(methyleneamine)-9-methylenehydroxy-4,7-dithiadecane (Et(HO)N 3 S 2 amp) and an eleven-membered pendant arm macrocyclic ligand 6,10-dimethyl-6,10-bis(methyleneamine)-1,4-dithia-8-azaacycloundec-7-ene (dmatue). The complexes [Co(Et(HO)3ϩ (2), in which the alcohol is coordinated to the metal ion, and [Co(dmatue)Cl] 2ϩ (4) were isolated and characterized. Et(HO)N 3 S 2 amp also undergoes complexation with cobalt() to produce two isomers endo- [Co(Et(HO)(exo-3), both with an uncoordinated alcohol group. endo-3 has the alcohol positioned cis, and exo-3 trans, to the sixth metal coordination site. Reaction of 1 with isobutyraldehyde, paraformaldehyde and base in dimethylformamide results in the encapsulated complex [Co(1,5,5,9,13,7,11,]-docosa-3,14-diene)](ClO 4 ) 3 ؒ2H 2 O ([Co(Me 6 docosadieneN 4 S 2 )] 3ϩ (5). All complexes have been characterized by single crystal X-ray study. The low-temperature (11 K) absorption spectrum of 1 has been measured in Nafion films with spin-allowed

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Sepulchrate: a macrobicyclic nitrogen cage for metal ions

Cited by 192 publications

References 2 publications

Electron transfer reactions of nickel complexes of 1,4,7-triazacyclodecane

Electron transfer reactions of nickel complexes of 1,4,7-triazacyclodecane

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Embracing ligands. A synthetic strategy towards new nitrogen–thioether multidentate ligands and characterization of the cobalt(iii) complexes

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