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Organomagnesium clusters: Structure, stability, and bonding in archetypal models |
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| Authors: | J Oscar C Jiménez-Halla Miquel Solà |
| Institution: | a Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden b Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Scheikundig Laboratorium der Vrije Universiteit, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands c Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, E-17071 Girona, Catalonia, Spain |
| Abstract: | 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 C2h, D2h, and Td symmetry. The most stable structure for (MgCl2)4 is D2h, the one for (MgH2)4 is C2h, and that of (CH3MgCl)4 is Td. 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 ΔVelstat (60% of all bonding terms ΔVelstat + ?Eoi) although the orbital interaction ?Eoi also provides an important contribution (40%). |
| Keywords: | Bond theory Density functional calculations Grignard reagents Magnesium Polar bonds |
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