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• W2004707304 abstract "The 16 e half-sandwich complexes [M(Cp*){E2C2(B10H10)}], (E = S, Se, M = Rh, Ir), and [M(η6-p-cymene){S2C2(B10H10)}] (M = Ru, Os) react with acetylene, propyne, and 3-methoxypropyne to give 18 e complexes, each containing a metal–boron bond (see scheme). Insertion of the alkyne into one of the metal–chalcogen bonds is followed by B−H activation, transfer of one hydrogen atom from the carborane through the metal to the terminal carbon of the alkyne and concomitant ortho-metalation of the carborane. The addition reactions of the 16 e half-sandwich complexes [M(η5-Cp*){E2C2(B10H10)}] (Cp*=pentamethylcyclopentadienyl: 1 S: E=S, M=Rh; 2 S: E=S; M=Ir; 2 Se: E=Se, M=Ir) and [M(η6-p-cymene){S2C2(B10H10)}] (p-cymene=4-isopropyltoluene; 3 S: M=Ru; 4 S: M=Os), with acetylene, propyne, and 3-methoxypropyne lead to the 18 e complexes 5–19 with a metal–boron bond in each case. The reactions start with an insertion of the alkyne into one of the metal–chalcogen bonds, followed by B−H activation, transfer of one hydrogen atom from the carborane via the metal to the terminal carbon of the alkyne, and concomitant ortho-metalation of the carborane. The E-η2-CC and the C(1)B units are arranged either cisoid or transoid at the metal. X-ray structural analyses are reported for one of the starting 16 e complexes (4 S), the cisoid complex 12 S (from 2 S and HC≡C-CH3), and the transoid complexes 9 S and 14 S (from 1 S and HC≡C-CH2OMe, and from 3 S and HC≡CH, respectively). All new complexes 5–19 were characterized by NMR spectroscopy (1H, 11B, 13C, and 77Se and 103Rh NMR spectroscopy when appropriate). Die Additionsreaktionen der 16 e-Halbsandwich-Komplexe [M(η5-Cp*){E2C2(B10H10)}] (1 S: E=S, M=Rh; 2 S: E=S; M=Ir; 2 Se: E=Se, M=Ir) und [M(η6-p-cymene){S2C2(B10H10)}] (p-cymene=4-isopropyltoluol; 3 S: M=Ru; 4 S: M=Os), mit Acetylen, Propin und 3-Methoxypropin führen zu 18 e-Komplexen 5–19, wobei sich in allen Fällen eine Metall-Bor-Bindung ausbildet. Die Reaktionen beginnen mit einer Einschiebung des Alkins in eine der Metall-Chalkogen Bindungen, dann folgen B−H Aktivierung, Übertragung eines H-Atoms vom Carboran über das Metall zum terminalen Kohlenstoff des Alkins und damit gleichzeitig ortho-Metallierung des Carborans. Die E-η2-CC-Gruppierung des Alkins und die C(1)B Bindung des Carborans können am Metall entweder cisoid oder transoid zueinander angeordnet sein. Es wurden Röntgenstrukturanalysen durchgeführt an einem der 16 e-Ausgangskomplexe (4 S), an dem cisoid-Komplex 12 S (aus 2 S und HC≡C-CH3) und den transoid-Komplexen 9 S und 14 S (aus 1 S und HC≡C-CH2OMe bzw. aus 3 S und HC≡CH). Alle neuen Additionsverbindungen 5–19 wurden durch Multikern-magnetische Resonanz-Spektroskopie (1H-, 11B-, 13C-, und 77Se- und 103Rh-NMR, wo angebracht) charakterisiert." @default.
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• W2004707304 date "2002-01-18" @default.
• W2004707304 modified "2023-10-12" @default.
• W2004707304 title "Metal-Induced B−H Activation: Addition of Acetylene, Propyne, or 3-Methoxypropyne to Rh(Cp*), Ir(Cp*), Ru(p-cymene), and Os(p-cymene) Half-Sandwich Complexes Containing a Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dichalcogenolato Ligand" @default.
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• W2004707304 doi "https://doi.org/10.1002/1521-3765(20020118)8:2<388::aid-chem388>3.0.co;2-u" @default.
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