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
N1 - Funding Information:
This research was financially supported by Grant-in-Aids for Scientific Research on Priority Area (Nos. 14078101 and 14078211 “Reaction Control of Dynamic Complexes”) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.
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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U2 - 10.1016/j.jorganchem.2006.07.047
DO - 10.1016/j.jorganchem.2006.07.047
M3 - Article
AN - SCOPUS:33845619129
VL - 692
SP - 1
EP - 9
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-3
ER -