Three-Center M-H-B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

We describe new compounds of stoichiometry M(CH₂NMe₂BH₃)₃ (M = Ti, Cr, and Co), each of which contains three chelating boranatodimethylaminomethyl (BDAM) ligands. In all three compounds, the BDAM anion, which is isoelectronic and isostructural with the neopentyl group, is bound to the metal center at one end by a metal-carbon σ bond and at the other by one three-center M-H-B interaction. The crystal structures show that the d¹ titanium(III) compound is trigonal prismatic (or eight-coordinate, if two longer-ranged M···H interactions with the BH₃ groups are included), whereas the d³ chromium(III) compound and the d⁶ cobalt(III) compounds are both fac-octahedral. The Cr and Co compounds exhibit two rapid dynamic processes in solution: exchange between the Δ and Λ enantiomers and exchange of the terminal and bridging hydrogen atoms on boron. For the Co complex, the barrier for Δ/Λ exchange (ΔG^⧧₂₉₈ = 10.1 kcal mol^-1) is significantly smaller than those seen in other octahedral cobalt(III) compounds; DFT calculations suggest that Bailar twist and dissociative pathways for Δ/Λ exchange are both possible mechanisms. The UV-vis absorption spectra of the cobalt(III) and chromium(III) species show that the ligand field splittings Δ_o caused by the M-H-B interactions are unexpectedly large, thus placing them high on the spectrochemical series (near ammonia and alkyl groups); their nephelauxetic effect is also large. The DFT calculations suggest that these properties of M-H-B interactions are in part a consequence of their three-center nature, which delocalizes electron density away from the metal center and reduces electron-electron repulsions.