RESUMO
We describe the synthesis and characterization of the quadruply-bonded dimer Mo2(CH2NMe2BH3)4 in which each molybdenum(II) center is bound to two chelating boranatodimethylaminomethyl (BDAM) ligands. The BDAM anions bind to the metal at one end by a metal-carbon σ bond and at the other by a three-center M-H-B interaction. Each BDAM ligand chelates to a single Mo atom so that the metal-metal bond is unbridged; the Mo-Mo distance is 2.114(2) Å. Structural and solution NMR data, analyzed via McConnell's equation and supported by DFT calculations, show that the magnetic anisotropies associated with highly polarizable and π-bonding ligands (such as chloride groups and aryl rings) can greatly affect the NMR chemical shifts of reporter groups, so that ignoring their contributions leads to significant overestimates of the anisotropy due just to the metal-metal bond. We propose a method to quantify and correct for the magnetic anisotropy effects arising from the ligands. Application of this method to Mo2(BDAM)4 indicates that the magnetic anisotropy of the Mo-Mo quadruple bond in this molecule is about -800 × 10-36 m3 molecule-1. Anisotropies significantly higher than this value (as sometimes reported in the prior literature) are most likely incorrect.
RESUMO
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 Δo 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.