New class of diiron dithiolates related to the Fe-only hydrogenase active site: Synthesis and characterization of [Fe2(SR)2(CNME)7]2+

Joshua D. Lawrence; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/ic025919t

New class of diiron dithiolates related to the Fe-only hydrogenase active site: Synthesis and characterization of [Fe₂(SR)2(CNME)₇]²⁺

Joshua D. Lawrence, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

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

Abstract

Electron-rich polyisocyano derivatives Fe₂(S₂C_nH_2n) (CO)_6-χ(CNMe)_χ (x ∼ 4) undergo oxidatively induced (FeCp₂⁺) reaction with additional CNMe to give [Fe₂(SR)₂(CNMe)₇] (PF₆)₂, a new class of iron thiolates. Crystallographic characterization established that the 34 e^- dinuclear core resembles the oxidized (H₂-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 Å. Oxidation of the phenylthiolate Fe₂(SPh)₂(CO)₂(CNMe)₄ led to mononuclear [Fe(SPh)(CNMe)₅]-(PF₆), which is analogous to [Fe₂(SR)₂(CNMe)₁₀] (PF₆)₂ formed upon treatment of [Fe₂(S₂C₃He)(CNMe)₇] (PF₆)₂ with excess CNMe.

Original language	English (US)
Pages (from-to)	6193-6195
Number of pages	3
Journal	Inorganic Chemistry
Volume	41
Issue number	24
DOIs	https://doi.org/10.1021/ic025919t
State	Published - Dec 2 2002

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic025919t

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@article{0521bf5dda0b41a98a11a70a46e145b3,

title = "New class of diiron dithiolates related to the Fe-only hydrogenase active site: Synthesis and characterization of [Fe2(SR)2(CNME)7]2+",

abstract = "Electron-rich polyisocyano derivatives Fe2(S2CnH2n) (CO)6-χ(CNMe)χ (x ∼ 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe2(SR)2(CNMe)7] (PF6)2, a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the oxidized (H2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 {\AA}. Oxidation of the phenylthiolate Fe2(SPh)2(CO)2(CNMe)4 led to mononuclear [Fe(SPh)(CNMe)5]-(PF6), which is analogous to [Fe2(SR)2(CNMe)10] (PF6)2 formed upon treatment of [Fe2(S2C3He)(CNMe)7] (PF6)2 with excess CNMe.",

author = "Lawrence, {Joshua D.} and Rauchfuss, {Thomas B.} and Wilson, {Scott R.}",

year = "2002",

month = dec,

day = "2",

doi = "10.1021/ic025919t",

language = "English (US)",

volume = "41",

pages = "6193--6195",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - New class of diiron dithiolates related to the Fe-only hydrogenase active site

T2 - Synthesis and characterization of [Fe2(SR)2(CNME)7]2+

AU - Lawrence, Joshua D.

AU - Rauchfuss, Thomas B.

AU - Wilson, Scott R.

PY - 2002/12/2

Y1 - 2002/12/2

N2 - Electron-rich polyisocyano derivatives Fe2(S2CnH2n) (CO)6-χ(CNMe)χ (x ∼ 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe2(SR)2(CNMe)7] (PF6)2, a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the oxidized (H2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 Å. Oxidation of the phenylthiolate Fe2(SPh)2(CO)2(CNMe)4 led to mononuclear [Fe(SPh)(CNMe)5]-(PF6), which is analogous to [Fe2(SR)2(CNMe)10] (PF6)2 formed upon treatment of [Fe2(S2C3He)(CNMe)7] (PF6)2 with excess CNMe.

AB - Electron-rich polyisocyano derivatives Fe2(S2CnH2n) (CO)6-χ(CNMe)χ (x ∼ 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe2(SR)2(CNMe)7] (PF6)2, a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the oxidized (H2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 Å. Oxidation of the phenylthiolate Fe2(SPh)2(CO)2(CNMe)4 led to mononuclear [Fe(SPh)(CNMe)5]-(PF6), which is analogous to [Fe2(SR)2(CNMe)10] (PF6)2 formed upon treatment of [Fe2(S2C3He)(CNMe)7] (PF6)2 with excess CNMe.

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