ja051748q_si_002.cif (31.78 kB)

Synthesis and Crystal Structure of an Open Capsule-Type Octanuclear Heterometallic Sulfide Cluster with a Linked Incomplete Double Cubane Framework without an Intramolecular Inversion Center

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posted on 19.10.2005, 00:00 by Bunsho Kure, Seiji Ogo, Daisuke Inoki, Hidetaka Nakai, Kiyoshi Isobe, Shunichi Fukuzumi
An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me6){P(OMe)3}{MoO(μ3-S)3}(CuI)2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl26-C6Me6){P(OMe)3}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS3]2- as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a CuI building block to form a trigonal planar (μ-S)2CuI unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order:  [RuCl26-C6Me6){P(OMe)3}] (1a, mononuclear) → [Ru(η6-C6Me6){P(OMe)3}{MoOS(μ2-S)2}] (2a, dinuclear) → [Ru(η6-C6Me6){P(OMe)3}{MoO(μ2-S)23-S)}CuI] (3a, butterfly-type trinuclear) → [Ru(η6-C6Me6){P(OMe)3}{MoO(μ3-S)3}(CuI)2]2 (5). When P(OMe)3 was replaced by P(OEt)3, which is more bulky than P(OMe)3, in the starting ruthenium building block [RuCl26-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3}{MoO(μ3-S)3}(CuI)2] (6) was generated, owing to the steric effect of P(OEt)3.