Iron(II) complexes of 2-mercaptopyridine as rubredoxin site analogues

Partha Halder; Santanu Ghorai; Sridhar Banerjee; Biswajit Mondal; Atanu Rana

doi:10.1039/c7dt02645e

Iron(II) complexes of 2-mercaptopyridine as rubredoxin site analogues

Partha Halder, Santanu Ghorai, Sridhar Banerjee, Biswajit Mondal, Atanu Rana

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The synthesis, characterization and reactivity studies of iron(ii) complexes [Fe^II(PySH)₄](OTf)₂, 1-(OTf)₂, [Fe^II(PySH)₄](ClO)₄, 1-(ClO₄)₂, and [Fe^II(PyS)₂]_n, (2), of a 2-mercaptopyridine (PySH) ligand are discussed. The X-ray crystal structures of both 1-(OTf)₂ and 1-(ClO₄)₂ reveal a distorted tetrahedral geometry at the iron(ii) center with identical constituents. All the pyridine nitrogen atoms are protonated and thiolate ions are coordinated to the iron(ii) center. The structure and function of complex 1-(OTf)₂ or 1-(ClO₄)₂ resembles the active site of rubredoxin. Complex 2 has octahedral geometry at the iron(ii) center forming a 1-D coordination polymer. Complex 1-(OTf)₂ exhibits a high positive redox potential (E_1/2 = 0.23 V vs. Ag/AgCl) which reduces to -0.12 V in the presence of triethylamine under an inert atmosphere. This change of the redox potential is highly reversible in the presence of a weak acid such as p-toluenesulfonic acid, pTsOH. DFT studies show that the complex cation [Fe^II(PySH)₄]²⁺ upon treatment with a base converts to its anionic congener, [Fe^II(PyS)₄]^2-, via the deprotonation of the pyridinium moiety. The iron(ii) complexes readily react with molecular oxygen to yield the corresponding iron(iii) complex, which rapidly decays to form pyridine disulphide (Py₂S₂) and an iron(ii) complex.

Original language	English
Pages (from-to)	13739-13744
Number of pages	6
Journal	Dalton Transactions
Volume	46
Issue number	40
DOIs	https://doi.org/10.1039/c7dt02645e
State	Published - 1 Jan 2017
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1039/c7dt02645e

Cite this

@article{06d47aa3b117442295e7d515bd35849b,

title = "Iron(II) complexes of 2-mercaptopyridine as rubredoxin site analogues",

abstract = "The synthesis, characterization and reactivity studies of iron(ii) complexes [FeII(PySH)4](OTf)2, 1-(OTf)2, [FeII(PySH)4](ClO)4, 1-(ClO4)2, and [FeII(PyS)2]n, (2), of a 2-mercaptopyridine (PySH) ligand are discussed. The X-ray crystal structures of both 1-(OTf)2 and 1-(ClO4)2 reveal a distorted tetrahedral geometry at the iron(ii) center with identical constituents. All the pyridine nitrogen atoms are protonated and thiolate ions are coordinated to the iron(ii) center. The structure and function of complex 1-(OTf)2 or 1-(ClO4)2 resembles the active site of rubredoxin. Complex 2 has octahedral geometry at the iron(ii) center forming a 1-D coordination polymer. Complex 1-(OTf)2 exhibits a high positive redox potential (E1/2 = 0.23 V vs. Ag/AgCl) which reduces to -0.12 V in the presence of triethylamine under an inert atmosphere. This change of the redox potential is highly reversible in the presence of a weak acid such as p-toluenesulfonic acid, pTsOH. DFT studies show that the complex cation [FeII(PySH)4]2+ upon treatment with a base converts to its anionic congener, [FeII(PyS)4]2-, via the deprotonation of the pyridinium moiety. The iron(ii) complexes readily react with molecular oxygen to yield the corresponding iron(iii) complex, which rapidly decays to form pyridine disulphide (Py2S2) and an iron(ii) complex.",

author = "Partha Halder and Santanu Ghorai and Sridhar Banerjee and Biswajit Mondal and Atanu Rana",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

month = jan,

day = "1",

doi = "10.1039/c7dt02645e",

language = "English",

volume = "46",

pages = "13739--13744",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "40",

}

TY - JOUR

T1 - Iron(II) complexes of 2-mercaptopyridine as rubredoxin site analogues

AU - Halder, Partha

AU - Ghorai, Santanu

AU - Banerjee, Sridhar

AU - Mondal, Biswajit

AU - Rana, Atanu

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The synthesis, characterization and reactivity studies of iron(ii) complexes [FeII(PySH)4](OTf)2, 1-(OTf)2, [FeII(PySH)4](ClO)4, 1-(ClO4)2, and [FeII(PyS)2]n, (2), of a 2-mercaptopyridine (PySH) ligand are discussed. The X-ray crystal structures of both 1-(OTf)2 and 1-(ClO4)2 reveal a distorted tetrahedral geometry at the iron(ii) center with identical constituents. All the pyridine nitrogen atoms are protonated and thiolate ions are coordinated to the iron(ii) center. The structure and function of complex 1-(OTf)2 or 1-(ClO4)2 resembles the active site of rubredoxin. Complex 2 has octahedral geometry at the iron(ii) center forming a 1-D coordination polymer. Complex 1-(OTf)2 exhibits a high positive redox potential (E1/2 = 0.23 V vs. Ag/AgCl) which reduces to -0.12 V in the presence of triethylamine under an inert atmosphere. This change of the redox potential is highly reversible in the presence of a weak acid such as p-toluenesulfonic acid, pTsOH. DFT studies show that the complex cation [FeII(PySH)4]2+ upon treatment with a base converts to its anionic congener, [FeII(PyS)4]2-, via the deprotonation of the pyridinium moiety. The iron(ii) complexes readily react with molecular oxygen to yield the corresponding iron(iii) complex, which rapidly decays to form pyridine disulphide (Py2S2) and an iron(ii) complex.

AB - The synthesis, characterization and reactivity studies of iron(ii) complexes [FeII(PySH)4](OTf)2, 1-(OTf)2, [FeII(PySH)4](ClO)4, 1-(ClO4)2, and [FeII(PyS)2]n, (2), of a 2-mercaptopyridine (PySH) ligand are discussed. The X-ray crystal structures of both 1-(OTf)2 and 1-(ClO4)2 reveal a distorted tetrahedral geometry at the iron(ii) center with identical constituents. All the pyridine nitrogen atoms are protonated and thiolate ions are coordinated to the iron(ii) center. The structure and function of complex 1-(OTf)2 or 1-(ClO4)2 resembles the active site of rubredoxin. Complex 2 has octahedral geometry at the iron(ii) center forming a 1-D coordination polymer. Complex 1-(OTf)2 exhibits a high positive redox potential (E1/2 = 0.23 V vs. Ag/AgCl) which reduces to -0.12 V in the presence of triethylamine under an inert atmosphere. This change of the redox potential is highly reversible in the presence of a weak acid such as p-toluenesulfonic acid, pTsOH. DFT studies show that the complex cation [FeII(PySH)4]2+ upon treatment with a base converts to its anionic congener, [FeII(PyS)4]2-, via the deprotonation of the pyridinium moiety. The iron(ii) complexes readily react with molecular oxygen to yield the corresponding iron(iii) complex, which rapidly decays to form pyridine disulphide (Py2S2) and an iron(ii) complex.

UR - http://www.scopus.com/inward/record.url?scp=85031725426&partnerID=8YFLogxK

U2 - 10.1039/c7dt02645e

DO - 10.1039/c7dt02645e

M3 - Article

C2 - 28956575

AN - SCOPUS:85031725426

SN - 1477-9226

VL - 46

SP - 13739

EP - 13744

JO - Dalton Transactions

JF - Dalton Transactions

IS - 40

ER -

Iron(II) complexes of 2-mercaptopyridine as rubredoxin site analogues

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this