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.
An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(3)-S)(3)}(CuI)(2)](2) (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl(2)(eta(6)-C(6)Me(6)){P(OMe)(3)}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS(3)](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 (mu-S)(2)CuI unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl(2)(eta(6)-C(6)Me(6)){P(OMe)(3)}] (1a, mononuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoOS(mu(2)-S)(2)}] (2a, dinuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(2)-S)(2)(mu(3)-S)}CuI] (3a, butterfly-type trinuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(3)-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 [RuCl(2)(eta(6)-C(6)Me(6)){P(OEt)(3)}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(eta(6)-C(6)Me(6)){P(OEt)(3)}{MoO(mu(3)-S)(3)}(CuI)(2)] (6) was generated, owing to the steric effect of P(OEt)(3).
Kure
Bunsho
B
Department of Material and Life Science, Graduate School of Engineering, Osaka University, PRESTO and SORST, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan.
Ogo
Seiji
S
Inoki
Daisuke
D
Nakai
Hidetaka
H
Isobe
Kiyoshi
K
Fukuzumi
Shunichi
S
D003460:Crystallization; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
D009942:Organometallic Compounds; D013440:Sulfides; D028561:Transition Elements