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Issue 6, 2014
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Isolation of the key intermediates of base-promoted borylene–carbonyl coupling reactions

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Abstract

The terminal alkylborylene complex [(η5–C5H5)(OC)2Mn[double bond, length as m-dash]BtBu] (1) reacts with trimethylphosphine and CO to form a borylene–carbonyl coupling product [(η5–C5H5)(OC)Mn{κ2–C,C′–C(O)B(tBu)(PMe3)C(O)}] (3). This reactivity can be extended to nitrogen- and carbon-based ligands to form similar complexes [(η5–C5H5)(OC)Mn{κ2–C,C′–C(O)B(tBu)(L)C(O)}] (L = DMAP, 7, and IMe, 8). The key intermediates of these reactions were found to be neutral, Lewis base-stabilized borylenes of the form [(η5–C5H5)(OC)2Mn[double bond, length as m-dash]B(tBu)(L)] (L = 4-dimethylaminopyridine (DMAP), 4, 3,5-lutidine, 5 and :C[N(Me)CH]2 (IMe), 6, which have been isolated and fully characterized. They can be synthesized from simple addition of the base to the parent borylene 1. The coordination of the base to the boron center seems to facilitate a rearrangement of the t-butyl borylene substituent.

Graphical abstract: Isolation of the key intermediates of base-promoted borylene–carbonyl coupling reactions

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Publication details

The article was received on 17 Jan 2014, accepted on 14 Feb 2014 and first published on 17 Feb 2014


Article type: Edge Article
DOI: 10.1039/C4SC00183D
Citation: Chem. Sci., 2014,5, 2271-2276
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    Isolation of the key intermediates of base-promoted borylene–carbonyl coupling reactions

    H. Braunschweig, T. Kramer, K. Radacki, R. Shang, E. Siedler and C. Werner, Chem. Sci., 2014, 5, 2271
    DOI: 10.1039/C4SC00183D

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