Iron Carbide-Sulfide Carbonyl Clusters

Liang Liu; Thomas B. Rauchfuss; Toby J. Woods

doi:10.1021/acs.inorgchem.9b01231

Iron Carbide-Sulfide Carbonyl Clusters

Liang Liu, Thomas B. Rauchfuss, Toby J. Woods

Chemistry

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

Abstract

Described is the preparation of the first iron carbide-sulfides. The cluster [Fe₆C(CO)₁₅(SO₂)]^2- ([2]^2-), which is generated quantitatively from [Fe₆C(CO)₁₆]^2- ([1]^2-), was O-methylated to give the sulfinite [2Me]^-. Demethoxylation of [2Me]^- with BF₃ gave the face-capped octahedral cluster Fe₆C(CO)₁₅(SO) (3). In solution, 3 spontaneously converted to the sulfide Fe₆C(CO)₁₆(S) (4), an edge-fused double cluster with Fe₅C and Fe₃S subunits. Although 4 undergoes 1e^- reduction reversibly, 2e^- reduction (or base hydrolysis) of 4 gives closo-[Fe₆C(CO)₁₄(S)]^2- ([5]^2-). The synthetic entries into the Fe₆CS_x manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.

Original language	English (US)
Pages (from-to)	8271-8274
Number of pages	4
Journal	Inorganic Chemistry
Volume	58
Issue number	13
DOIs	https://doi.org/10.1021/acs.inorgchem.9b01231
State	Published - Jul 1 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.9b01231

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title = "Iron Carbide-Sulfide Carbonyl Clusters",

abstract = "Described is the preparation of the first iron carbide-sulfides. The cluster [Fe6C(CO)15(SO2)]2- ([2]2-), which is generated quantitatively from [Fe6C(CO)16]2- ([1]2-), was O-methylated to give the sulfinite [2Me]-. Demethoxylation of [2Me]- with BF3 gave the face-capped octahedral cluster Fe6C(CO)15(SO) (3). In solution, 3 spontaneously converted to the sulfide Fe6C(CO)16(S) (4), an edge-fused double cluster with Fe5C and Fe3S subunits. Although 4 undergoes 1e- reduction reversibly, 2e- reduction (or base hydrolysis) of 4 gives closo-[Fe6C(CO)14(S)]2- ([5]2-). The synthetic entries into the Fe6CSx manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.",

author = "Liang Liu and Rauchfuss, {Thomas B.} and Woods, {Toby J.}",

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doi = "10.1021/acs.inorgchem.9b01231",

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AU - Liu, Liang

AU - Rauchfuss, Thomas B.

AU - Woods, Toby J.

PY - 2019/7/1

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N2 - Described is the preparation of the first iron carbide-sulfides. The cluster [Fe6C(CO)15(SO2)]2- ([2]2-), which is generated quantitatively from [Fe6C(CO)16]2- ([1]2-), was O-methylated to give the sulfinite [2Me]-. Demethoxylation of [2Me]- with BF3 gave the face-capped octahedral cluster Fe6C(CO)15(SO) (3). In solution, 3 spontaneously converted to the sulfide Fe6C(CO)16(S) (4), an edge-fused double cluster with Fe5C and Fe3S subunits. Although 4 undergoes 1e- reduction reversibly, 2e- reduction (or base hydrolysis) of 4 gives closo-[Fe6C(CO)14(S)]2- ([5]2-). The synthetic entries into the Fe6CSx manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.

AB - Described is the preparation of the first iron carbide-sulfides. The cluster [Fe6C(CO)15(SO2)]2- ([2]2-), which is generated quantitatively from [Fe6C(CO)16]2- ([1]2-), was O-methylated to give the sulfinite [2Me]-. Demethoxylation of [2Me]- with BF3 gave the face-capped octahedral cluster Fe6C(CO)15(SO) (3). In solution, 3 spontaneously converted to the sulfide Fe6C(CO)16(S) (4), an edge-fused double cluster with Fe5C and Fe3S subunits. Although 4 undergoes 1e- reduction reversibly, 2e- reduction (or base hydrolysis) of 4 gives closo-[Fe6C(CO)14(S)]2- ([5]2-). The synthetic entries into the Fe6CSx manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.

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Iron Carbide-Sulfide Carbonyl Clusters

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