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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 Fe6CS x manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.

SUBMITTER: Liu L 

PROVIDER: S-EPMC6602809 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Iron Carbide-Sulfide Carbonyl Clusters.

Liu Liang L   Rauchfuss Thomas B TB   Woods Toby J TJ  

Inorganic chemistry 20190611 13


Described is the preparation of the first iron carbide-sulfides. The cluster [Fe<sub>6</sub>C(CO)<sub>15</sub>(SO<sub>2</sub>)]<sup>2-</sup> ([2]<sup>2-</sup>), which is generated quantitatively from [Fe<sub>6</sub>C(CO)<sub>16</sub>]<sup>2-</sup> ([1]<sup>2-</sup>), was O-methylated to give the sulfinite [2Me]<sup>-</sup>. Demethoxylation of [2Me]<sup>-</sup> with BF<sub>3</sub> gave the face-capped octahedral cluster Fe<sub>6</sub>C(CO)<sub>15</sub>(SO) (3). In solution, 3 spontaneously conver  ...[more]

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