Rational Synthesis and Crystal Structures of Heterometallic-Heterochalcogenido Cubane-Type Clusters [(Cp<sup>*</sup>M)<sub>2</sub>(MoOCl<sub>2</sub>){MoCl<sub>2</sub>(dmf)}(μ<sub>3</sub>-S)<sub>2</sub>(μ<sub>3</sub>-Se)<sub>2</sub>] (M=Rh, Ir)
作者:Hidetake Seino、Masanobu Hidai、Yasushi Mizobe
DOI:10.1246/cl.2002.920
日期:2002.9
Reactions of [MoO(dmf)3}2(μ2-S)2]I2 with [(Cp*MCl)2(μ2-SeH)2] (M=Rh, Ir) in the presence of NMe4Cl gave mixed-metal sulfido-selenido clusters [(Cp*M)2(MoOCl2)MoCl2(dmf)}(μ3-S)2(μ3-Se)2], whose cubane-type core structures have been demonstrated in detail by X-ray crystallography.
Reactions of hydrosulfido- and hydroselenido-bridged dinuclear Ir, Rh, and Ru complexes with SbCl3 and BiCl3 affording mixed-metal sulfido and selenido clusters containing both noble metals and Group 15 metals
A new versatile method to synthesize a series of noble metal-Group 15 metal chalcogenido clusters has been found. Thus, treatment of the hydrosulfido- or hydroselenido-bridged dinuclear complexes [Cp*MCl(mu-EH)(2)MCp*Cl] (M = lr, Rh; E = S, Se; Cp* = eta(5)-C5Me5), [CpdegreesRuCl(mu-SH)(2)RuCpdegreesCl] (Cpdegrees= eta(5)-C5EtMe4), and [Ru(L)Cl(mu-SH)(2)Ru(L)Cl] (L = eta(6)-C6Me5H) with M'Cl-3 (M'=Sb, Bi) in THF at room temperature afforded smoothly the clusters [Cp*MCl(mu-EM'Cl-2)(2)MCP*Cl], [CpdegreesRuCl(mu-SM'Cl-2)(2)RuCpdegreesCl], and [Ru(L)Cl(mu-SM'Cl-2)(2)Ru(L)Cl] through dehydrochlorination. The X-ray analyses of eleven new clusters clarified the details of their structures consisting of the cubane-type M2M'2ECl2 cores resulting from the presence of weak MCL...M' bonding interactions in addition to the normal M-E, M-Cl, and M'-E bonds. (C) 2004 Elsevier B.V. All rights reserved.