Chelate ring sequence effects on thermodynamic, kinetic and electron-transfer properties of copper(ii/i) systems involving macrocyclic ligands with S4 and NS3 donor setsElectronic supplementary information (ESI) available: Tables S1–14: tabulations of experimental rate constants. See http://www.rsc.org/suppdata/dt/b3/b300602f/

Galijašević, Semira; Krylova, Ksenia; Koenigbauer, Michael J.; Jaeger, Gregory; Bushendorf, Jeffery D.; Heeg, Mary Jane; Ochrymowycz, L. A.; Täschner, Michael; Rorabacher, D. B.

doi:10.1039/b300602f

Cited by 22 publications

(31 citation statements)

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“…This system exchanged electrons very rapidly and, therefore, is treated in the section on rapidly reacting systems below. Two other macrocyclic complexes with three thiaether sulfurs and one amine nitrogen have recently been reported by Galijasevic et al, 152 both being 14-membered macrocycles. The difference between these two ligands is that [14]aneNS 3 -a has the more common chelate ring sequence 5,6,5,6 while [14]aneNS 3 -b has the sequence 5,5,6,6 ( Figure 11).…”

Section: Thiaether Sulfur−amine Nitrogen Mixed Donor Ligand Systemsmentioning

confidence: 90%

Electron Transfer by Copper Centers

2004

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Section: Thiaether Sulfur−amine Nitrogen Mixed Donor Ligand Systemsmentioning

confidence: 90%

Electron Transfer by Copper Centers

2004

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“…Previous investigations in our laboratory have examined the various thermodynamic and kinetic properties of a variety of Cu(II/I) complexes formed with macrocyclic polythioethers 1-14 and mixed donor ligands [15][16][17][18] with a specific focus on understanding the effect of conformational constraints on the electron-transfer kinetic behavior. The majority of these studies has involved complexes formed with tetrathioether ligands with variable geometric constraints imposed either by substituted peripheral groups or alterations in the ring size.…”

Section: Introductionmentioning

confidence: 99%

“…In pursuing the rationale that the avoidance of donor atom inversion and metal-solvent bond rupture might represent primary factors in promoting faster electron transfer, we recently studied the electron-transfer behavior of a Cu(II/I) system involving an 18-membered macrocycle containing six sulfur donor atoms, [18]aneS 6 (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(ii/i) complexes with sexadentate macrocyclic ligands. [Cu^II/I([18]aneS₄N₂)] and [Cu^II/I([18]aneS₄O₂)]

et al. 2007

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Studies have been conducted on the copper complexes formed with two sexadentate macrocyclic ligands containing four thioether sulfur donor atoms plus either two nitrogen or two oxygen donor atoms on opposing sides of the ring. The resulting two ligands, L, designated as [18]aneS(4)N(2) and [18]aneS(4)O(2), respectively, represent homologues of the previously studied Cu(ii/i) system with a macrocycle having six sulfur donor atoms, [18]aneS(6). Crystal structures of [Cu(II)([18]aneS(4)O(2))](ClO(4))(2) and [Cu(I)([18]aneS(4)O(2))]ClO(4) have been determined in this work. Comparison of the structures of all three systems reveals that the oxidized complexes are six coordinate with two coordinate bonds undergoing rupture upon reduction. However, the geometric changes accompanying electron transfer appear to differ for the three systems. The stability constants and electrochemical properties of both of the heteromacrocyclic complexes have been determined in acetonitrile and the Cu(II/I)L electron-transfer kinetics have been studied in the same solvent using six different counter reagents for each system. The electron self-exchange rate constants have then been calculated using the Marcus cross relationship. The results are compared to other Cu(II/I)L systems in terms of the effect of ligand geometric changes upon the overall kinetic behavior.

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“…57 In other oxidases, a positively charged residue is present around the flavin N5, 58 and is postulated to stabilize the superoxide anion (formed during the first stepwise electron transfer to dioxygen) via electrostatic interactions. [58][59][60][61][62][63] In vanillyl alcohol oxidase-type flavoproteins, it was observed that a covalent linkage between the flavin cofactor and the protein increases the redox potential of the flavin significantly, limiting the number of feasible electron acceptors. 32,64 It was also observed that bicovalently linked flavin cofactors have a very open active site, while retaining the cofactor in position for catalysis, allowing them to accept bulky substrates.…”

Section: ]mentioning

confidence: 99%

“…When the electron transfer steps and reversible chemical transformations occur in a consecutive manner, the mechanism can be represented as a square-scheme. [50][51][52][53][54][55][56][57][58][59][60][61][62] The complete electrochemical reduction mechanism of riboflavin in DMSO is given in Scheme 2. Fl…”

Section: Digital Simulation Of CV Datamentioning

confidence: 99%

Electrochemistry of flavins

Tan¹

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A thesis submitted to the Nanyang Technological University in fulfillment of the requirements for the degree of Doctor of Philosophy of Chemistry First and foremost, I would like to thank Nanyang Technological University (NTU) for awarding me the Nanyang President's Graduate Scholarship, and giving me opportunities to attending 2 conferences which has broadened my horizons both scientifically and personally. I would also like to thank my PhD supervisor, Assoc. Prof. Richard David Webster, for accepting me into his group without prior experience, for providing guidance over these 4 years, for giving me space and freedom to explore the field, for understanding, for never having any harsh words and being really great to talk to even for non-electrochemistry topics. Much love to my lunch buddies, Gwen, Shu Jun, Novi, for being the best part of these 4 years, making me look forward to school every day. Also, I am really thankful to my student Jiamin, for being so reliable, meticulous and determined. I could not have done it without you, and could not have asked for a better student! To all Gwen's ex-students and my ex-lunch buddies (Marcus, Shu Jun, Li Zhen, Li Lin and Wen Hui), it has been great knowing all of you! Special thanks to Shu Jun and Novi for the last few months, starving yourselves till 2 pm to lunch with me, to Novi for stepping up without complaints to help me with data collection, to Yanni for always being so kind and sweet, and to Diane for understanding! Also, thanks to Shu Hui for our dinners, for working late together and for the trips home. To Colin, thanks for your friendship and "thanks" for scaring me while making sure I am not holding any glassware. To Weejian, thanks for your kind notes of encouragement during my FYP days, and being the kind of friend that sticks around. To Boon Hong, thanks for being mature and understanding, for helping me with ithenticate II and so much more, you are truly a much better person than you are given credit for! You are friends I wish I knew earlier and hope to keep for many years to come! To my other labmates,

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Cited by 22 publications

References 51 publications

Electron Transfer by Copper Centers

Electron Transfer by Copper Centers

Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(ii/i) complexes with sexadentate macrocyclic ligands. [Cu^II/I([18]aneS₄N₂)] and [Cu^II/I([18]aneS₄O₂)]

Electrochemistry of flavins

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Cited by 22 publications

References 51 publications

Electron Transfer by Copper Centers

Electron Transfer by Copper Centers

Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(ii/i) complexes with sexadentate macrocyclic ligands. [CuII/I([18]aneS4N2)] and [CuII/I([18]aneS4O2)]

Electrochemistry of flavins

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Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(ii/i) complexes with sexadentate macrocyclic ligands. [Cu^II/I([18]aneS₄N₂)] and [Cu^II/I([18]aneS₄O₂)]