Jump to main content
Jump to site search


Diborane heterolysis: breaking and making B–B bonds at magnesium

Author affiliations

Abstract

Reaction of the dimeric β-diketiminato magnesium hydride [(BDI)MgH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2) with bis-pinacolatodiborane (B2pin2) resulted in B–O bond activation and formation of a magnesium complex of an unusual borylborohydride anion. In contrast, similar treatment of the mononuclear organomagnesium [{BDI}Mg(n-Bu)] with 4,4,4′,4′,6,6′-hexamethyl-2,2′-bi(1,3,2-dioxaborinane) (B2hex2) provided a B(sp2)–B(sp3) diborane anion, [(hex)BB(n-Bu)(hex)], with a constitution which is analogous to that formed in the previously reported reaction with bis(pinacolato)diboron (B2pin2). Subsequent addition of 4-dimethylaminopyridine to a solution of this compound induced alkylborane displacement and provided a magnesium boryl derivative containing a terminal Mg–B(hex) interaction (Mg–B 2.319(3) Å), a result which reinforces the generality of this approach for the synthesis of boryl anions by B–B bond heterolysis. Further studies of the reactivity of the initially formed B(sp2)–B(sp3) anions with diborane small molecules also resulted in alkylborane displacement and the production of triboron anions, which are propagated by contiguous and electron precise (2c–2e) B–B–B interactions.

Graphical abstract: Diborane heterolysis: breaking and making B–B bonds at magnesium

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Apr 2018, accepted on 09 May 2018 and first published on 09 May 2018


Article type: Paper
DOI: 10.1039/C8DT01451E
Citation: Dalton Trans., 2018, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    Diborane heterolysis: breaking and making B–B bonds at magnesium

    A. Pécharman, M. S. Hill and M. F. Mahon, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01451E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements