Structurally defined ring-opening and insertion of pinacolborane into aluminium-nitrogen bonds of sterically demanding dialkylaluminium amides

Pollard, Victoria A. and Kennedy, Alan R. and McLellan, Ross and Ross, Duncan and Tuttle, Tell and Mulvey, Robert E. (2021) Structurally defined ring-opening and insertion of pinacolborane into aluminium-nitrogen bonds of sterically demanding dialkylaluminium amides. European Journal of Inorganic Chemistry, 2021 (1). pp. 50-53. ISSN 1434-1948 (https://doi.org/10.1002/ejic.202000919)

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Abstract

Dialkylaluminium amides iBu 2Al(TMP) and iBu 2Al(HMDS) can perform catalytic hydroboration of ketones with pinacolborane to form the expected boronic esters. However, repeating the same reactions stoichiometrically without a ketone leads unexpectedly to ring-opening of pinacolborane and insertion of its open chain into the Al−N(amido) bond. To date there has been limited knowledge on decomposition pathways of HBpin despite its prominent role in hydroboration chemistry. X-ray crystallography shows these mixed Al−B products [iBu 2Al{OC(Me) 2C(Me) 2O}B(H)(NR 2)] 2 (NR 2=TMP or HMDS) form dimers with an (AlO) 2 core and terminal B−N bonds. Since the bond retention (B−H) and bond breaking (B−O) in these transformations seemed surprising, DFT calculations run using M11/6-31G(d,p) gave an energy profile consistent with a σ-bond metathesis mechanism where London dispersion interactions between iBu and (amide) Me groups play an important stabilising role in the final outcome.

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