[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

Takashi Komuro; Hiroyuki Kawaguchi; Jianping Lang; Takayuki Nagasawa; Kazuyuki Tatsumi

doi:10.1016/j.jorganchem.2006.07.047

[MoFe₃S₄]³⁺ and [MoFe₃S₄]²⁺ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

Takashi Komuro, Hiroyuki Kawaguchi, Jianping Lang, Takayuki Nagasawa, Kazuyuki Tatsumi

Research output: Contribution to journal › Article

9 Citations (Scopus)

Abstract

A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp^*MoFe₃S₄L_n]^m (Cp^* = η⁵-C₅Me₅; L = S^tBu, SPh, Cl, I, n = 3, m = 1-; L_n = I₂(P^tBu₃), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh₄)[Cp^*MoFe₃S₄(S^tBu)₃] (2) was isolated from a self-assembly reaction of Cp^*Mo(S^tBu)₃ (1), FeCl₃, LiS^tBu, and S₈ followed by cation exchange with PPh₄Br in CH₃CN, while an analogous cluster (PPh₄)[Cp^*MoFe₃S₄(SPh)₃] (3) was obtained from the Cp^*MoCl₄/FeCl₃/LiSPh/PPh₄Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh₄)[Cp^*MoFe₃S₄Cl₃] (4), which was in turn converted to (PPh₄)[Cp^*MoFe₃S₄I₃] (5) by the reaction with NaI. A neutral cubane cluster Cp^*MoFe₃S₄I₂(P^tBu₃) (6) was generated upon treating 5 with P^tBu₃. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe₄S₄(ArNC)₉Cl (7), a similar reduction reaction of 5 produced [Cp^*MoFe₃S₄(ArNC)₇]I (8), where the MoFe₃S₄ core was retained. The crystal structures of 4-6, and 8 were determined by the X-ray analysis.

Original language	English
Pages (from-to)	1-9
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	692
Issue number	1-3
DOIs	https://doi.org/10.1016/j.jorganchem.2006.07.047
Publication status	Published - 2007 Jan 1
Externally published	Yes

Keywords

Cubane cluster
Cyclopentadienyl
Iron: sulfide
Molybdenum

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Komuro, T., Kawaguchi, H., Lang, J., Nagasawa, T., & Tatsumi, K. (2007). [MoFe₃S₄]³⁺ and [MoFe₃S₄]²⁺ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety. Journal of Organometallic Chemistry, 692(1-3), 1-9. https://doi.org/10.1016/j.jorganchem.2006.07.047

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title = "[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety",

abstract = "A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp*MoFe3S4Ln]m (Cp* = η5-C5Me5; L = StBu, SPh, Cl, I, n = 3, m = 1-; Ln = I2(PtBu3), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh4)[Cp*MoFe3S4(StBu)3] (2) was isolated from a self-assembly reaction of Cp*Mo(StBu)3 (1), FeCl3, LiStBu, and S8 followed by cation exchange with PPh4Br in CH3CN, while an analogous cluster (PPh4)[Cp*MoFe3S4(SPh)3] (3) was obtained from the Cp*MoCl4/FeCl3/LiSPh/PPh4Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh4)[Cp*MoFe3S4Cl3] (4), which was in turn converted to (PPh4)[Cp*MoFe3S4I3] (5) by the reaction with NaI. A neutral cubane cluster Cp*MoFe3S4I2(PtBu3) (6) was generated upon treating 5 with PtBu3. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe4S4(ArNC)9Cl (7), a similar reduction reaction of 5 produced [Cp*MoFe3S4(ArNC)7]I (8), where the MoFe3S4 core was retained. The crystal structures of 4-6, and 8 were determined by the X-ray analysis.",

keywords = "Cubane cluster, Cyclopentadienyl, Iron: sulfide, Molybdenum",

author = "Takashi Komuro and Hiroyuki Kawaguchi and Jianping Lang and Takayuki Nagasawa and Kazuyuki Tatsumi",

year = "2007",

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doi = "10.1016/j.jorganchem.2006.07.047",

language = "English",

volume = "692",

pages = "1--9",

journal = "Journal of Organometallic Chemistry",

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TY - JOUR

T1 - [MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

AU - Komuro, Takashi

AU - Kawaguchi, Hiroyuki

AU - Lang, Jianping

AU - Nagasawa, Takayuki

AU - Tatsumi, Kazuyuki

PY - 2007/1/1

Y1 - 2007/1/1

N2 - A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp*MoFe3S4Ln]m (Cp* = η5-C5Me5; L = StBu, SPh, Cl, I, n = 3, m = 1-; Ln = I2(PtBu3), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh4)[Cp*MoFe3S4(StBu)3] (2) was isolated from a self-assembly reaction of Cp*Mo(StBu)3 (1), FeCl3, LiStBu, and S8 followed by cation exchange with PPh4Br in CH3CN, while an analogous cluster (PPh4)[Cp*MoFe3S4(SPh)3] (3) was obtained from the Cp*MoCl4/FeCl3/LiSPh/PPh4Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh4)[Cp*MoFe3S4Cl3] (4), which was in turn converted to (PPh4)[Cp*MoFe3S4I3] (5) by the reaction with NaI. A neutral cubane cluster Cp*MoFe3S4I2(PtBu3) (6) was generated upon treating 5 with PtBu3. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe4S4(ArNC)9Cl (7), a similar reduction reaction of 5 produced [Cp*MoFe3S4(ArNC)7]I (8), where the MoFe3S4 core was retained. The crystal structures of 4-6, and 8 were determined by the X-ray analysis.

AB - A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp*MoFe3S4Ln]m (Cp* = η5-C5Me5; L = StBu, SPh, Cl, I, n = 3, m = 1-; Ln = I2(PtBu3), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh4)[Cp*MoFe3S4(StBu)3] (2) was isolated from a self-assembly reaction of Cp*Mo(StBu)3 (1), FeCl3, LiStBu, and S8 followed by cation exchange with PPh4Br in CH3CN, while an analogous cluster (PPh4)[Cp*MoFe3S4(SPh)3] (3) was obtained from the Cp*MoCl4/FeCl3/LiSPh/PPh4Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh4)[Cp*MoFe3S4Cl3] (4), which was in turn converted to (PPh4)[Cp*MoFe3S4I3] (5) by the reaction with NaI. A neutral cubane cluster Cp*MoFe3S4I2(PtBu3) (6) was generated upon treating 5 with PtBu3. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe4S4(ArNC)9Cl (7), a similar reduction reaction of 5 produced [Cp*MoFe3S4(ArNC)7]I (8), where the MoFe3S4 core was retained. The crystal structures of 4-6, and 8 were determined by the X-ray analysis.

KW - Cubane cluster

KW - Cyclopentadienyl

KW - Iron: sulfide

KW - Molybdenum

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