Organomagnesium clusters: Structure, stability, and bonding in archetypal models

作者：Jimenez Halla J Oscar C; Bickelhaupt F Matthias^*; Sola Miquel

来源：Journal of Organometallic Chemistry, 2011, 696(25): 4104-4111.

DOI：10.1016/j.jorganchem.2011.06.014

• Bond theory
• Density functional calculations
• Grignard reagents
• Magnesium
• Polar bonds

We have studied the molecular structure and the nature of the chemical bond in the monomers and tetramers of the Grignard reagent CH3MgCl as well as MgX2 (X = H, Cl, and CH3) at the BP86/TZ2P level of theory. For the tetramers, we discuss the stability of three possible molecular structures of C-2h, D-2h, and T-d symmetry. The most stable structure for (MgCl2)(4) is D-2h, the one for (MgH2)(4) is C-2h, and that of (CH3MgCl)(4) is T-d. The latter is 38 kcal/mol more stable with chlorines in bridge positions and methyl groups coordinated to a Mg vertex than vice versa. We find through a quantitative energy decomposition analysis (EDA) that the tetramerization energy is predominantly composed of electrostatic attraction Delta V-elstat (60% of all bonding terms Delta V-elstat + Delta E-oi) although the orbital interaction Delta E-oi also provides an important contribution (40%).

• 出版日期2011-12-15