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.
Redox reactions, substitutions, and metalations are reported for the n class="Chemical">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 Fe6Ccore decorated with μ3-S and μ2-SO2 ligands. These experiments were undertaken in an effort to connect organometallic clusters to FeMoco.
Authors: Subramaniam Kuppuswamy; Joshua D Wofford; Chris Joseph; Zhu-Lin Xie; Azim K Ali; Vincent M Lynch; Paul A Lindahl; Michael J Rose Journal: Inorg Chem Date: 2017-04-25 Impact factor: 5.165
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Authors: Myles J Drance; Charles C Mokhtarzadeh; Mohand Melaimi; Douglas W Agnew; Curtis E Moore; Arnold L Rheingold; Joshua S Figueroa Journal: Angew Chem Int Ed Engl Date: 2018-05-24 Impact factor: 15.336