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Reactions of [Fe6C(CO)14(S)]2-: Cluster Growth, Redox, Sulfiding.

ABSTRACT: Redox reactions, substitutions, and metalations are reported for the iron carbido sulfide [Fe6C(CO)14(S)]2- ([1]2-). Dianion [1]2- oxidized to [Fe6C(CO)16(S)]0 ([2]0) upon treatment with of [Fe(C5H5)2]BF4 or HBF4 (H2 formation) under an atmosphere of CO. Reaction of [2]0 with tBuNC gave [Fe6C(S)(CO)13(tBuNC)5], consisting of Fe5C(CO)13 and [Fe(tBuNC)5]2+ subunits linked by a μ3-S2-. The Fe7CS cluster [Fe7C(CO)17(S)]2- formed upon treatment of (Ph4P)2[1] with Fe(benzylideneacetone)(CO)3. The Fe7 species is an edge-fused cluster with [Fe6C(CO)10(μ-CO)4] and Fe(CO)3 subunits joined by μ3-S and two Fe-Fe bonds. The analogous reaction using Mo(CO)4(norbornadiene) gave [MoFe6C(CO)18(S)]2-. In this cluster, the Mo center is located in the octahedral subunit. Treatment of [1]2- with SO2 afforded [Fe6C(S)(SO2)(CO)13]2-. This cluster features an Fe6C core decorated with μ3-S and μ2-SO2 ligands. These experiments were undertaken in an effort to connect organometallic clusters to FeMoco.

SUBMITTER: Liu L 

PROVIDER: S-EPMC8054992 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Reactions of [Fe<sub>6</sub>C(CO)<sub>14</sub>(S)]<sup>2-</sup>: Cluster Growth, Redox, Sulfiding.

Liu Liang L   Woods Toby J TJ   Rauchfuss Thomas B TB  

European journal of inorganic chemistry 20200904 36

Redox reactions, substitutions, and metalations are reported for the iron carbido sulfide [Fe<sub>6</sub>C(CO)<sub>14</sub>(S)]<sup>2-</sup> ([<b>1</b>]<sup>2-</sup>). Dianion [<b>1</b>]<sup>2-</sup> oxidized to [Fe<sub>6</sub>C(CO)<sub>16</sub>(S)]<sup>0</sup> ([<b>2</b>]<sup>0</sup>) upon treatment with of [Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>]BF<sub>4</sub> or HBF<sub>4</sub> (H<sub>2</sub> formation) under an atmosphere of CO. Reaction of [<b>2</b>]<sup>0</sup> with <i>t</i>BuNC gave [  ...[more]

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