TY - JOUR
T1 - 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
AU - Kure, Bunsho
AU - Ogo, Seiji
AU - Inoki, Daisuke
AU - Nakai, Hidetaka
AU - Isobe, Kiyoshi
AU - Fukuzumi, Shunichi
PY - 2005/10/19
Y1 - 2005/10/19
N2 - An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 2(η6-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 Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl2(η6-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)2(μ 3-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)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 [RuCl 2(η6-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.
AB - An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(η6-C6Me 6){P(OMe)3}{MoO(μ3-S)3}(Cul) 2]2 (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl 2(η6-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 Cul building block to form a trigonal planar (μ-S) 2Cul unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl2(η6-C6Me6){P(OMe) 3}] (1a, mononuclear) → [Ru(η6-C 6Me6){P(OMe)3}{MoOS(μ2-S) 2}] (2a, dinuclear) → [Ru(η6-C6Me 6){P(OMe)3}{MoO-(μ2-S)2(μ 3-S)}Cul] (3a, butterfly-type trinuclear) → [Ru(η 6-C6Me6){P(OMe)3} {MoO(μ3-S)3}(Cul)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 [RuCl 2(η6-C6Me6){P(OEt)3}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(η6-C6Me6){P(OEt)3} {MoO(μ3-S)3}(Cul)2] (6) was generated, owing to the steric effect of P(OEt)3.
UR - http://www.scopus.com/inward/record.url?scp=26844532145&partnerID=8YFLogxK
U2 - 10.1021/ja051748q
DO - 10.1021/ja051748q
M3 - Article
C2 - 16218631
AN - SCOPUS:26844532145
SN - 0002-7863
VL - 127
SP - 14366
EP - 14374
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 41
ER -