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Syntheses and characterization of new vinyl-borylene complexes by the hydroboration of alkynes with [(μ3-BH)(Cp*RuCO) 2(μ-CO)Fe(CO)3]
Kuppusamy Yuvaraj, Bijan Mondal, Amrita S. Sikder,
Published in
2013
Volume: 19
   
Issue: 7
Pages: 2337 - 2343
Abstract
Room temperature photolysis of a triply-bridged borylene complex, [(μ3-BH)(Cp*RuCO)2(μ-CO)Fe(CO)3] (1 a; Cp*=C5Me5), in the presence of a series of alkynes, 1,2-diphenylethyne, 1-phenyl-1-propyne, and 2-butyne led to the isolation of unprecedented vinyl-borylene complexes (Z)-[(Cp*RuCO) 2(μ-CO)B(CR)(CHR′)] (2: R, R′=Ph; 3: R=Me, R′=Ph; 4: R, R′=Me). This reaction permits a hydroboration of alkyne through an anti-Markovnikov addition. In stark contrast, in the presence of phenylacetylene, a metallacarborane, closo-[1,2-(Cp*Ru) 2(μ-CO)2{Fe2(CO)5}-4-Ph-4,5- C2BH2] (5 a), is formed. A plausible mechanism has been proposed for the formation of vinyl-borylene complexes, which is supported by density functional theory (DFT) methods. Furthermore, the calculated 11B NMR chemical shifts accurately reflect the experimentally measured shifts. All the new compounds have been characterized in solution by mass spectrometry and IR, 1H, 11B, and 13C NMR spectroscopies and the structural types were unequivocally established by crystallographic analysis of 2, 5 a, and 5 b. Unique metal-borylene complexes: Photolysis of a triply bridged borylene complex [(μ3-BH) (Cp*RuCO)2(μ-CO)Fe(CO)3] (Cp*= η5-C5Me5) with various internal alkynes led to hydroboration yielding new vinyl-borylene complexes (see figure). A plausible mechanism has been proposed for the formation of vinyl-borylene complexes, which is supported by density functional theory (DFT) methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
About the journal
JournalChemistry - A European Journal
ISSN09476539
Open AccessNo
Concepts (22)
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    2-BUTYNE
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    Alkynes
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    BORYLENE COMPLEXES
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    BORYLENES
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    CRYSTALLOGRAPHIC ANALYSIS
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    Density functional theory methods
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    HYDROBORATION
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    Internal alkynes
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    Nmr chemical shifts
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    Phenylacetylenes
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    Plausible mechanisms
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    Room temperature
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    STRUCTURAL TYPE
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    Aromatic hydrocarbons
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    Boron
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    Density functional theory
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    Iron compounds
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    Mass spectrometry
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    Nuclear magnetic resonance spectroscopy
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    Photolysis
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    Ruthenium
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    Acetylene