Surprising Condensation Reactions of the Azadithiolate Cofactor

Fanjun Zhang; Casseday P. Richers; Toby J. Woods; Thomas B. Rauchfuss

doi:10.1002/anie.202108135

Surprising Condensation Reactions of the Azadithiolate Cofactor

Fanjun Zhang, Casseday P. Richers, Toby J. Woods, Thomas B. Rauchfuss

Chemistry

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

Abstract

Azadithiolate, a cofactor found in all [FeFe]-hydrogenases, is shown to undergo acid-catalyzed rearrangement. Fe₂[(SCH₂)₂NH](CO)₆ self-condenses to give Fe₆[(SCH₂)₃N]₂(CO)₁₇. The reaction, which is driven by loss of NH₄⁺, illustrates the exchange of the amine group. X-ray crystallography reveals that three Fe₂(SR)₂(CO)_x butterfly subunits interconnected by the aminotrithiolate [N(CH₂S)₃]³⁻. Mechanistic studies reveal that Fe₂[(SCH₂)₂NR](CO)₆ participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru₂[(SCH₂)₂NH](CO)₆ also rearranges, but proceeds further to give derivatives with Ru-alkyl bonds Ru₆[(SCH₂)₃N][(SCH₂)₂NCH₂]S(CO)₁₇ and [Ru₂[(SCH₂)₂NCH₂](CO)₅]₂S.

Original language	English (US)
Pages (from-to)	20744-20747
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	38
DOIs	https://doi.org/10.1002/anie.202108135
State	Published - Sep 13 2021

Keywords

carbonyls
cofactors
hydrogenase
iron
thiolate

ASJC Scopus subject areas

Catalysis
General Chemistry

Online availability

10.1002/anie.202108135

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title = "Surprising Condensation Reactions of the Azadithiolate Cofactor",

abstract = "Azadithiolate, a cofactor found in all [FeFe]-hydrogenases, is shown to undergo acid-catalyzed rearrangement. Fe2[(SCH2)2NH](CO)6 self-condenses to give Fe6[(SCH2)3N]2(CO)17. The reaction, which is driven by loss of NH4+, illustrates the exchange of the amine group. X-ray crystallography reveals that three Fe2(SR)2(CO)x butterfly subunits interconnected by the aminotrithiolate [N(CH2S)3]3−. Mechanistic studies reveal that Fe2[(SCH2)2NR](CO)6 participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru2[(SCH2)2NH](CO)6 also rearranges, but proceeds further to give derivatives with Ru-alkyl bonds Ru6[(SCH2)3N][(SCH2)2NCH2]S(CO)17 and [Ru2[(SCH2)2NCH2](CO)5]2S.",

keywords = "carbonyls, cofactors, hydrogenase, iron, thiolate",

author = "Fanjun Zhang and Richers, {Casseday P.} and Woods, {Toby J.} and Rauchfuss, {Thomas B.}",

note = "Funding Information: This research was supported by the U.S. National Institutes of Health. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

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AU - Zhang, Fanjun

AU - Richers, Casseday P.

AU - Woods, Toby J.

AU - Rauchfuss, Thomas B.

PY - 2021/9/13

Y1 - 2021/9/13

N2 - Azadithiolate, a cofactor found in all [FeFe]-hydrogenases, is shown to undergo acid-catalyzed rearrangement. Fe2[(SCH2)2NH](CO)6 self-condenses to give Fe6[(SCH2)3N]2(CO)17. The reaction, which is driven by loss of NH4+, illustrates the exchange of the amine group. X-ray crystallography reveals that three Fe2(SR)2(CO)x butterfly subunits interconnected by the aminotrithiolate [N(CH2S)3]3−. Mechanistic studies reveal that Fe2[(SCH2)2NR](CO)6 participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru2[(SCH2)2NH](CO)6 also rearranges, but proceeds further to give derivatives with Ru-alkyl bonds Ru6[(SCH2)3N][(SCH2)2NCH2]S(CO)17 and [Ru2[(SCH2)2NCH2](CO)5]2S.

AB - Azadithiolate, a cofactor found in all [FeFe]-hydrogenases, is shown to undergo acid-catalyzed rearrangement. Fe2[(SCH2)2NH](CO)6 self-condenses to give Fe6[(SCH2)3N]2(CO)17. The reaction, which is driven by loss of NH4+, illustrates the exchange of the amine group. X-ray crystallography reveals that three Fe2(SR)2(CO)x butterfly subunits interconnected by the aminotrithiolate [N(CH2S)3]3−. Mechanistic studies reveal that Fe2[(SCH2)2NR](CO)6 participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru2[(SCH2)2NH](CO)6 also rearranges, but proceeds further to give derivatives with Ru-alkyl bonds Ru6[(SCH2)3N][(SCH2)2NCH2]S(CO)17 and [Ru2[(SCH2)2NCH2](CO)5]2S.

KW - carbonyls

KW - cofactors

KW - hydrogenase

KW - iron

KW - thiolate

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Surprising Condensation Reactions of the Azadithiolate Cofactor

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