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The thermolysis of arachno-1 [(Cp*Ru)2(B3H8)(CS2H)] in the presence of tellurium powder yielded a series of ruthenium trithia-borinane complexes: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BH}] 2, [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3B(SMe)}] 3, and [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BH}] 4. Compounds 2–4 were considered as ruthenium trithia-borinane complexes, where the central six-membered ring {C2BS3} adopted a boat conformation. Compounds 2–4 were similar to our recently reported ruthenium diborinane complex [(Cp*Ru){(η2-SCHS)CH2S2(BH2)2}]. Unlike diborinane, where the central six-membered ring {CB2S3} adopted a chair conformation, compounds 2–4 adopted a boat conformation. In an attempt to convert arachno-1 into a closo or nido cluster, we pyrolyzed it in toluene. Interestingly, the reaction led to the isolation of a capped butterfly cluster, [(Cp*Ru)2(B3H5)(CS2H2)] 5. All the compounds were characterized by 1H, 11B{1H}, and 13C{1H} NMR spectroscopy and mass spectrometry. The molecular structures of complexes 2, 3, and 5 were also determined by single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

In an objective to synthesize metallaheteroboranes containing heavier chalcogen atoms, we performed the reaction of dimetallaborane analogues of pentaborane(9) with various chalcogen sources. As a result, the thermolysis of nido -[1,2-(Cp*RuH) 2 B 3 H 7 ], 1 (Cp* = η 5 -C 5 Me 5 ) with mixture of S and Se powder was carried out, that led to the isolation of half sandwich dimetallaheteroborane arachno -[(1,2-Cp*Ru) 2 B 2 H 6 S 2 ], 2 . On the other hand, the reaction of nido - 1 with diorganyldichalcogenide ligands, [Ph 2 E 2 ] afforded chalcogen bridged half sandwich complexes [(2,3-Cp*Ru) 2 B 3 H 6 (μ-η 1 -EPh)], 4a-c ( 4a : E = S; 4b : E = Se and 4c : E = Te). Compound 2 can be derived from a closo- snub disphenoid by removing a 5-connect vertex followed by the removal of a 3-connect vertex. Compound 4a – c can be described as nido -square pyramidal structures, isoelectronic and isostructural with nido - 1 . All the compounds have been characterized by mass spectrometry, 1 H, 11 B and 13 C spectroscopy. Further, the geometry of compounds 2 , 3 , 4b and 4c were unequivocally established by crystallographic analysis. [ABSTRACT FROM AUTHOR]

A metal rich cluster made of Groups 8 and 9 metals was synthesized featuring a µ 5 -boride moiety. [Display omitted] • A new type of μ 5 -boride cluster [(IrCp*){Ru(CO) 2 }{Ru(CO) 3 } 3 (µ -H) 5 B 2 H 2 (μ 5 -B)] (1) is synthesised. • Cluster 1 is a unique boride derived from an eight-vertex closo -dodecadeltahedron by removal of one five-connected vertex followed by capping of a Ru(CO) 3 moiety. • Trimetallic and tetrametallic metallaboranes with a µ 3 -coordinated triply-bridged borylene moiety is also isolated. A series of metal-rich clusters of group 9 containing boride or borylene units have been isolated and structurally characterized. The thermolysis reaction of arachno- [IrCp*H 2 (B 3 H 7)] ( I ) with [Ru 3 (CO) 12 ] allowed to isolate the µ 5 -boride nido -[(IrCp*){Ru(CO) 2 }{Ru(CO) 3 } 3 (µ -H) 5 B 2 H 2 (μ 5 -B)] (1) and the tetrametallic cluster [(IrCp*) 2 {Ru(CO) 2 }{Ru(CO) 3 }(μ -CO) 2 (μ 3 -BH)] (2) with a µ 3 -coordinated triply-bridged borylene moiety. The geometry of cluster 1 can be derived from an eight-vertex closo -dodecadeltahedron by removal of one five-connected vertex followed by capping of a Ru(CO) 3 moiety. The borylene moiety (BH) of cluster 2 is connected in a μ 3 -fashion to the deltahedral face of a tetrametallic tetrahedron (Ir 2 Ru 2). To synthesize the Mn analogue of 2 , thermolysis reaction with [Mn 2 (CO) 10 ] was carried out, that afforded the trimetallic tetrahedral borylene [(IrCp*) 2 {MnH (CO) 3 }(μ -CO) 2 (μ 3 -BH)] (3) along with the known face-fused boride [{Ir(CO) 2 } 3 (IrCp*) 3 (μ 3 -CO)(μ -CO)(μ 5 -BH)] (4). Clusters 2 and 3 are the first triply-bridged borylenes having an Ir metal atom in the core. All these clusters were characterized by NMR (1H, 11B and 13C), infrared (IR) spectroscopies and mass spectrometry. The structure of cluster 1 was confirmed by X-ray diffraction analysis. In addition, density functional theory (DFT) calculations were conducted to interpret and study the nature of bonding and electronic structure of cluster 1. [ABSTRACT FROM AUTHOR]

Abstract: Mild thermolysis of arachno-[(Cp*RuCO)2B2H6], 1 in presence of GeCl2·dioxane yielded di-μ-germylene complex [(Cp*Ru)2(μ-GeCl2)2(CO)2], 2 (Cp* = η5-C5Me5). The molecular structure of 2 exhibits a diruthenium unit bridged by a pair of μ-GeCl2 moieties. The Cp* and the terminal CO ligands are oriented in anti fashion with respect to Ru–Ru bond. In addition, the reaction of 2 with arachno-[CpFe(CO)B3H8] (Cp = η5-C5H5) transformed to germenocene, [Cp2Ge:], 3 via an unstable intermediate [CpFe(CO)B2H5GeCl2], I. The 11B NMR spectroscopy was used as a tool to establish a probable reaction pathway for the formation of germenocene 3. Cluster 2 has been characterized by IR and NMR spectroscopy, and the geometric structure was unequivocally established by crystallographic analysis. [Copyright &y& Elsevier]