DERIVATIVES OF BOROLE .17. (ETA-5-[1-(DIISOPROPYLAMINO)BOROLE])METAL COMPLEXES - SYNTHESES, PROTONATION, INTERNAL-ROTATION

New complexes M(CO)4L (M = Cr, W), cis-M(CO)2L2 [M = Mo, W (not isolated)], and (COD)NiL have been prepared from the Diels-Alder dimer L2, where L is 1-(diisopropylamino)borole, C4H4BNiPr2. Complexes of L can be protonated at the nitrogen atom to give stable salts such as [Cr(CO)4(LH)]BF4, [Fe(CO)3(LH)]BF4, [(C6Me6)Ru(LH)]BF4, and [CpCo(LH)]BF4; B-N bond dissociation is not observed. Barriers to internal rotation have been determined by variable temperature NMR spectroscopy for Cr(CO)4L, (COD)NiL, and NiL2. Three processes have been identified: rotation of the NiPr2 group around the B-N bond, gear-mesh rotation of the isopropyl groups around the C-N bonds, and rotation of L with respect to the counter ligands.