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

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

doi:10.1002/ejic.202000736

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

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

Chemistry

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

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.

Original language	English (US)
Pages (from-to)	3460-3465
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Volume	2020
Issue number	36
Early online date	Sep 14 2020
DOIs	https://doi.org/10.1002/ejic.202000736
State	Published - Sep 30 2020

Keywords

Carbides
Cluster compounds
Iron
Nitrogenases
Sulfides

ASJC Scopus subject areas

Inorganic Chemistry

Online availability

10.1002/ejic.202000736

Library availability

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Cite this

@article{825eea8eea2840f2a44ec7e14f676e07,

title = "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.",

keywords = "Carbides, Cluster compounds, Iron, Nitrogenases, Sulfides",

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

note = "This research was supported by the U.S. National Institutes of Health through grant GM61153.",

year = "2020",

month = sep,

day = "30",

doi = "10.1002/ejic.202000736",

language = "English (US)",

volume = "2020",

pages = "3460--3465",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH",

number = "36",

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TY - JOUR

T1 - Reactions of [Fe6C(CO)14(S)]2–

T2 - Cluster Growth, Redox, Sulfiding

AU - Liu, Liang

AU - Woods, Toby J.

AU - Rauchfuss, Thomas B.

N1 - This research was supported by the U.S. National Institutes of Health through grant GM61153.

PY - 2020/9/30

Y1 - 2020/9/30

N2 - 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.

AB - 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.

KW - Carbides

KW - Cluster compounds

KW - Iron

KW - Nitrogenases

KW - Sulfides

UR - https://www.scopus.com/pages/publications/85090991965

UR - https://www.scopus.com/pages/publications/85090991965#tab=citedBy

U2 - 10.1002/ejic.202000736

DO - 10.1002/ejic.202000736

M3 - Article

C2 - 33883972

AN - SCOPUS:85090991965

SN - 1434-1948

VL - 2020

SP - 3460

EP - 3465

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 36

ER -