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A new strategy for the synthesis of a “cationic-cage” (CC-Ag) has been developed via metal–carbene (M–CNHC) bond formation followed by imine bond condensation. Reaction of a trigonal trisimidazolium salt H3L(PF6)3 functionalized with three flexible N-phenyl-aldehyde pendants with silver oxide yielded a trinuclear tricationic organometallic cage (OC-Ag). Subsequent treatment of the organometallic cage (OC-Ag) with 1,4-diaminobutane links the two tris–NHC ligands via imine bond condensation, which thus generates a 3D ‘cationic-cage’ (CC-Ag). Furthermore, post-synthetic replacement of the Ag(i) with Au(i) leading to the formation of CC-Au was achieved via trans-metalation, with the retention of the molecular architecture. [ABSTRACT FROM AUTHOR]

An unprecedented, 22-valence-electron triple-decker sandwich complex [(Cp*Mo)2{μ-η6:η6-B4H4Ru2(CO)6}], 2, has been prepared. In an effort to generate analogous triple-deckers with group 6 metal carbonyl fragments in the middle deck, we have isolated [(Cp*MoCO)2(μ-H)2B4H4], 3, that provides the first direct evidence for the missing link between [(Cp*MoCl)2B3H7] and [(Cp*Mo)2B5H9] clusters. [ABSTRACT FROM AUTHOR]

The reaction of metal carbonyl compounds with group 6 and 8 metallaboranes led us to report the synthesis and structural characterization of several novel mixed-metal chalcogenide tetrahedral clusters. Thermolysis of arachno-[(Cp*RuCO)2B2H6], 1, and [Os3(CO)12] in the presence of 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Os3(CO)9}S], 3, and [Cp*Ru(μ-H){Os3(CO)11}], 4. In a similar fashion, the reaction of [(Cp*Mo)2B5H9], 2, with [Ru3(CO)12] and 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Ru3(CO)9}S], 5, and conjuncto-[(Cp*Mo)2B5H8(μ-H){Ru3(CO)9}S], 6. Both compounds 3 and 5 can be described as 50-cve (cluster valence electron) mixed-metal chalcogenide clusters, in which a sulfur atom replaces one of the vertices of the tetrahedral core. Compounds 3 and 5 possess a [M3S] tetrahedral core, in which the sulfur is attached to an exo-metal fragment, unique in the [M3S] metal chalcogenide tetrahedral arrangements. All the compounds have been characterized by mass spectrometry, IR, and 1H, 11B and 13C NMR spectroscopy in solution, and the solid state structures were unequivocally established by crystallographic analysis of compounds 3, 5 and 6. [ABSTRACT FROM AUTHOR]

An unprecedented, 22-valence-electron triple-decker sandwich complex [(Cp*Mo)2{μ-η(6):η(6)-B4H4Ru2(CO)6}], 2, has been prepared. In an effort to generate analogous triple-deckers with group 6 metal carbonyl fragments in the middle deck, we have isolated [(Cp*MoCO)2(μ-H)2B4H4], 3, that provides the first direct evidence for the missing link between [(Cp*MoCl)2B3H7] and [(Cp*Mo)2B5H9] clusters.

The reaction of metal carbonyl compounds with group 6 and 8 metallaboranes led us to report the synthesis and structural characterization of several novel mixed-metal chalcogenide tetrahedral clusters. Thermolysis of arachno-[(Cp*RuCO)2B2H6], 1, and [Os3(CO)12] in the presence of 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Os3(CO)9}S], 3, and [Cp*Ru(μ-H){Os3(CO)11}], 4. In a similar fashion, the reaction of [(Cp*Mo)2B5H9], 2, with [Ru3(CO)12] and 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Ru3(CO)9}S], 5, and conjuncto-[(Cp*Mo)2B5H8(μ-H){Ru3(CO)9}S], 6. Both compounds 3 and 5 can be described as 50-cve (cluster valence electron) mixed-metal chalcogenide clusters, in which a sulfur atom replaces one of the vertices of the tetrahedral core. Compounds 3 and 5 possess a [M3S] tetrahedral core, in which the sulfur is attached to an exo-metal fragment, unique in the [M3S] metal chalcogenide tetrahedral arrangements. All the compounds have been characterized by mass spectrometry, IR, and (1)H, (11)B and (13)C NMR spectroscopy in solution, and the solid state structures were unequivocally established by crystallographic analysis of compounds 3, 5 and 6.