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

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.