TY - JOUR
T1 - Reversible Conversion of Disulfide/Dithiolate Occurring at a Vanadium(IV) Center
T2 - A Biomimetic System for Redox Exchange in Vanabin
AU - Lee, Cheng Hsun
AU - Lin, Ding Jyun
AU - Pan, Hung Ruei
AU - Wu, John
AU - Liu, Hsin Kuan
AU - Hsu, Hua Fen
N1 - Funding Information:
This work was supported by the Ministry of Science and Technology in Taiwan (MOST 110-2113-M-006-010).
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/12/12
Y1 - 2022/12/12
N2 - Ascidians use a class of cysteine-rich proteins generally referred to as vanabins to reduce vanadium ions, one of the many biological processes that involve the redox conversion between disulfide and dithiolate mediated by transition-metal ions. To further understand the nature of disulfide/dithiolate exchange facilitated by a vanadium center, we report herein a six-coordinate non-oxido VIVcomplex containing an unbound disulfide moiety, [VIV(PS3″)(PS1″S-S)] (1) (PS3″ = [P(C6H3-3-Me3Si-2-S)3]3-, where PS1″S-Sis a disulfide form of PS3″). Complex 1 is obtained from a reaction of previously reported [VV(PS3″)(PS2″SH)] (2) (PS2″SH= [P(C6H3-3-Me3Si-2-SH)(C6H3-3-Me3Si-2-S)2] with TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-yl)oxyl) via hydrogen atom transfer. Importantly, complex 1 can be reduced by two electrons to form an eight-coordinate VIVcomplex, [VIV(PS3″)2]2-(4). The reaction can be reversed through a two-electron oxidation process to regenerate complex 1. The redox pathways both proceed through a common intermediate, [V(PS3″)2]-(3), that has been previously reported as a resonance form of VV-dithiolate and a VIV-(thiolate)(thiyl-radical) species. This work demonstrates an unprecedented example of reversible disulfide/dithiolate interconversion mediated by a VIVcenter, as well as provides insights into understanding the function of VVreductases in vanabins.
AB - Ascidians use a class of cysteine-rich proteins generally referred to as vanabins to reduce vanadium ions, one of the many biological processes that involve the redox conversion between disulfide and dithiolate mediated by transition-metal ions. To further understand the nature of disulfide/dithiolate exchange facilitated by a vanadium center, we report herein a six-coordinate non-oxido VIVcomplex containing an unbound disulfide moiety, [VIV(PS3″)(PS1″S-S)] (1) (PS3″ = [P(C6H3-3-Me3Si-2-S)3]3-, where PS1″S-Sis a disulfide form of PS3″). Complex 1 is obtained from a reaction of previously reported [VV(PS3″)(PS2″SH)] (2) (PS2″SH= [P(C6H3-3-Me3Si-2-SH)(C6H3-3-Me3Si-2-S)2] with TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-yl)oxyl) via hydrogen atom transfer. Importantly, complex 1 can be reduced by two electrons to form an eight-coordinate VIVcomplex, [VIV(PS3″)2]2-(4). The reaction can be reversed through a two-electron oxidation process to regenerate complex 1. The redox pathways both proceed through a common intermediate, [V(PS3″)2]-(3), that has been previously reported as a resonance form of VV-dithiolate and a VIV-(thiolate)(thiyl-radical) species. This work demonstrates an unprecedented example of reversible disulfide/dithiolate interconversion mediated by a VIVcenter, as well as provides insights into understanding the function of VVreductases in vanabins.
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U2 - 10.1021/acs.inorgchem.2c03115
DO - 10.1021/acs.inorgchem.2c03115
M3 - Article
C2 - 36441974
AN - SCOPUS:85143420977
SN - 0020-1669
VL - 61
SP - 19882
EP - 19889
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 49
ER -