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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-S^2-. 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 |

REPOSITORIES: biostudies-literature

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