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The parent borylene (CAAC)(Me3P)BH, 1 (CAAC=cyclic alkyl(amino)carbene), acts both as a Lewis base and one‐electron reducing agent towards group 13 trichlorides (ECl3, E=B, Al, Ga, In), yielding the adducts 1‐ECl3 and increasing proportions of the radical cation [1]•+ for the heavier group 13 analogues. With boron trihalides (BX3, X=F, Cl, Br, I) 1 undergoes sequential adduct formation and halide...
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