Reaction Chemistry of the syn-[Mo2O2(μ-S)2(S2)(DMF)3] Complex with Cyanide and Catalytic Thiocyanate Formation

Sigridur G. Suman; Johanna M. Gretarsdottir; Paul E. Penwell; Jon P. Gunnarsson; Sindri Frostason; Sigridur Jonsdottir; Krishna K. Damodaran; Albert Hirschon

doi:10.1021/acs.inorgchem.0c00608

Reaction Chemistry of the syn-[Mo₂O₂(μ-S)₂(S₂)(DMF)₃] Complex with Cyanide and Catalytic Thiocyanate Formation

Sigridur G. Suman^*, Johanna M. Gretarsdottir, Paul E. Penwell, Jon P. Gunnarsson, Sindri Frostason, Sigridur Jonsdottir, Krishna K. Damodaran, Albert Hirschon

^*Corresponding author for this work

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

2 Citations (Scopus)

Abstract

Removal of cyanide as nontoxic thiocyanate under physiological conditions may serve as a catalytic detoxification route in vivo. Aqueous catalytic reaction conditions were explored where at the conditions employed the reaction proceeded to exhaustion in 1 h. The complex, syn-[Mo₂O₂(μ-S)₂(S₂)(DMF)₃] 1, participates in a ligand exchange reaction of the dimethylformamide ligands and cyanide. Simultaneous sulfur abstraction reaction from the terminal disulfide group forms thiocyanate and terminal sulfido ligand. Respective reaction rates for the two reactions appear competitive where different products were isolated solely based on change of reaction temperature. The approach to determine the number of cyanide ligands participating in the ligand exchange reaction by varying the stoichiometry and reaction temperature led to identification and isolation of tetranuclear complexes 2 and 5 and dinuclear complexes 3, 4, and 6. A synthesized and fully characterized thiocyanate analog of 6 (7) supports spectroscopic characterization of 6. The tetranuclear anion, [Mo₄O₄(μ-S)₆(CN)₄]^4-, 2, was crystallized from a reaction at ambient temperature. The dinuclear anion, [Mo₂O₂(μ-S)₂(S)(CN)₃]^3-, 3, was crystallized from similar reaction conditions at lower temperature. The reaction yield of thiocyanate obtained at pH of 7.4 and at 9.2 as a function of time, for several ratios of cyanide, favors the sulfur abstraction reaction at elevated pH. The sulfur abstraction reaction is the first step in a proposed mechanism of the reaction of cyanide and thiosulfate to form thiocyanate and sulfite by 1.

Original language	English
Pages (from-to)	7644-7656
Number of pages	13
Journal	Inorganic Chemistry
Volume	59
Issue number	11
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00608
Publication status	Published - 1 Jun 2020

Bibliographical note

Funding Information:
S.G.S. is thankful for support by the CounterACT Program, Office of the Director, National Institutes of Health (OD) and the National Institute of Neurological Disorders and Stroke (NINDS), grant no. 1R21NS067265. The contents presented are solely the responsibility of the authors and do not represent the official views of NIH/NINDS. Support from the University of Iceland, and from the Icelandic Centre of Research, grant no. 140945, is gratefully acknowledged. J.P.G., J.S.G., and S.F. acknowledge support from the Icelandic Student Innovation Fund, NSN2013 (Rannis). Jonina Sæunn Gudmundsdottir at the University of Iceland and Allen Dodge at SRI International are thanked for help with synthesis of 1 . Lindsey J. Monger and Linda A. Hancock at the University of Iceland are acknowledged for assistance with UV–vis data collection. Dr. Tobias Stuerzer, Bruker AXS, Germany, is acknowledged for his help with twin refinement of compound 3 .

Publisher Copyright:
© 2020 American Chemical Society.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acs.inorgchem.0c00608

Cite this

@article{8dd9e9dc412b4e08bbf4cef0bfbb1ce2,

title = "Reaction Chemistry of the syn-[Mo2O2(μ-S)2(S2)(DMF)3] Complex with Cyanide and Catalytic Thiocyanate Formation",

abstract = "Removal of cyanide as nontoxic thiocyanate under physiological conditions may serve as a catalytic detoxification route in vivo. Aqueous catalytic reaction conditions were explored where at the conditions employed the reaction proceeded to exhaustion in 1 h. The complex, syn-[Mo2O2(μ-S)2(S2)(DMF)3] 1, participates in a ligand exchange reaction of the dimethylformamide ligands and cyanide. Simultaneous sulfur abstraction reaction from the terminal disulfide group forms thiocyanate and terminal sulfido ligand. Respective reaction rates for the two reactions appear competitive where different products were isolated solely based on change of reaction temperature. The approach to determine the number of cyanide ligands participating in the ligand exchange reaction by varying the stoichiometry and reaction temperature led to identification and isolation of tetranuclear complexes 2 and 5 and dinuclear complexes 3, 4, and 6. A synthesized and fully characterized thiocyanate analog of 6 (7) supports spectroscopic characterization of 6. The tetranuclear anion, [Mo4O4(μ-S)6(CN)4]4-, 2, was crystallized from a reaction at ambient temperature. The dinuclear anion, [Mo2O2(μ-S)2(S)(CN)3]3-, 3, was crystallized from similar reaction conditions at lower temperature. The reaction yield of thiocyanate obtained at pH of 7.4 and at 9.2 as a function of time, for several ratios of cyanide, favors the sulfur abstraction reaction at elevated pH. The sulfur abstraction reaction is the first step in a proposed mechanism of the reaction of cyanide and thiosulfate to form thiocyanate and sulfite by 1.",

author = "Suman, {Sigridur G.} and Gretarsdottir, {Johanna M.} and Penwell, {Paul E.} and Gunnarsson, {Jon P.} and Sindri Frostason and Sigridur Jonsdottir and Damodaran, {Krishna K.} and Albert Hirschon",

note = "Funding Information: S.G.S. is thankful for support by the CounterACT Program, Office of the Director, National Institutes of Health (OD) and the National Institute of Neurological Disorders and Stroke (NINDS), grant no. 1R21NS067265. The contents presented are solely the responsibility of the authors and do not represent the official views of NIH/NINDS. Support from the University of Iceland, and from the Icelandic Centre of Research, grant no. 140945, is gratefully acknowledged. J.P.G., J.S.G., and S.F. acknowledge support from the Icelandic Student Innovation Fund, NSN2013 (Rannis). Jonina S{\ae}unn Gudmundsdottir at the University of Iceland and Allen Dodge at SRI International are thanked for help with synthesis of 1 . Lindsey J. Monger and Linda A. Hancock at the University of Iceland are acknowledged for assistance with UV–vis data collection. Dr. Tobias Stuerzer, Bruker AXS, Germany, is acknowledged for his help with twin refinement of compound 3 . Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jun,

day = "1",

doi = "10.1021/acs.inorgchem.0c00608",

language = "English",

volume = "59",

pages = "7644--7656",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Reaction Chemistry of the syn-[Mo2O2(μ-S)2(S2)(DMF)3] Complex with Cyanide and Catalytic Thiocyanate Formation

AU - Suman, Sigridur G.

AU - Gretarsdottir, Johanna M.

AU - Penwell, Paul E.

AU - Gunnarsson, Jon P.

AU - Frostason, Sindri

AU - Jonsdottir, Sigridur

AU - Damodaran, Krishna K.

AU - Hirschon, Albert

N1 - Funding Information: S.G.S. is thankful for support by the CounterACT Program, Office of the Director, National Institutes of Health (OD) and the National Institute of Neurological Disorders and Stroke (NINDS), grant no. 1R21NS067265. The contents presented are solely the responsibility of the authors and do not represent the official views of NIH/NINDS. Support from the University of Iceland, and from the Icelandic Centre of Research, grant no. 140945, is gratefully acknowledged. J.P.G., J.S.G., and S.F. acknowledge support from the Icelandic Student Innovation Fund, NSN2013 (Rannis). Jonina Sæunn Gudmundsdottir at the University of Iceland and Allen Dodge at SRI International are thanked for help with synthesis of 1 . Lindsey J. Monger and Linda A. Hancock at the University of Iceland are acknowledged for assistance with UV–vis data collection. Dr. Tobias Stuerzer, Bruker AXS, Germany, is acknowledged for his help with twin refinement of compound 3 . Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/6/1

Y1 - 2020/6/1

N2 - Removal of cyanide as nontoxic thiocyanate under physiological conditions may serve as a catalytic detoxification route in vivo. Aqueous catalytic reaction conditions were explored where at the conditions employed the reaction proceeded to exhaustion in 1 h. The complex, syn-[Mo2O2(μ-S)2(S2)(DMF)3] 1, participates in a ligand exchange reaction of the dimethylformamide ligands and cyanide. Simultaneous sulfur abstraction reaction from the terminal disulfide group forms thiocyanate and terminal sulfido ligand. Respective reaction rates for the two reactions appear competitive where different products were isolated solely based on change of reaction temperature. The approach to determine the number of cyanide ligands participating in the ligand exchange reaction by varying the stoichiometry and reaction temperature led to identification and isolation of tetranuclear complexes 2 and 5 and dinuclear complexes 3, 4, and 6. A synthesized and fully characterized thiocyanate analog of 6 (7) supports spectroscopic characterization of 6. The tetranuclear anion, [Mo4O4(μ-S)6(CN)4]4-, 2, was crystallized from a reaction at ambient temperature. The dinuclear anion, [Mo2O2(μ-S)2(S)(CN)3]3-, 3, was crystallized from similar reaction conditions at lower temperature. The reaction yield of thiocyanate obtained at pH of 7.4 and at 9.2 as a function of time, for several ratios of cyanide, favors the sulfur abstraction reaction at elevated pH. The sulfur abstraction reaction is the first step in a proposed mechanism of the reaction of cyanide and thiosulfate to form thiocyanate and sulfite by 1.

AB - Removal of cyanide as nontoxic thiocyanate under physiological conditions may serve as a catalytic detoxification route in vivo. Aqueous catalytic reaction conditions were explored where at the conditions employed the reaction proceeded to exhaustion in 1 h. The complex, syn-[Mo2O2(μ-S)2(S2)(DMF)3] 1, participates in a ligand exchange reaction of the dimethylformamide ligands and cyanide. Simultaneous sulfur abstraction reaction from the terminal disulfide group forms thiocyanate and terminal sulfido ligand. Respective reaction rates for the two reactions appear competitive where different products were isolated solely based on change of reaction temperature. The approach to determine the number of cyanide ligands participating in the ligand exchange reaction by varying the stoichiometry and reaction temperature led to identification and isolation of tetranuclear complexes 2 and 5 and dinuclear complexes 3, 4, and 6. A synthesized and fully characterized thiocyanate analog of 6 (7) supports spectroscopic characterization of 6. The tetranuclear anion, [Mo4O4(μ-S)6(CN)4]4-, 2, was crystallized from a reaction at ambient temperature. The dinuclear anion, [Mo2O2(μ-S)2(S)(CN)3]3-, 3, was crystallized from similar reaction conditions at lower temperature. The reaction yield of thiocyanate obtained at pH of 7.4 and at 9.2 as a function of time, for several ratios of cyanide, favors the sulfur abstraction reaction at elevated pH. The sulfur abstraction reaction is the first step in a proposed mechanism of the reaction of cyanide and thiosulfate to form thiocyanate and sulfite by 1.

UR - http://www.scopus.com/inward/record.url?scp=85085660245&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.0c00608

DO - 10.1021/acs.inorgchem.0c00608

M3 - Article

C2 - 32401019

AN - SCOPUS:85085660245

SN - 0020-1669

VL - 59

SP - 7644

EP - 7656

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -