Linear MgCp*2 vs Bent CaCp*2: London Dispersion, Ligand-Induced
Charge Localizations, and Pseudo-Pregostic C–H···Ca
Interactions
Posted on 2018-04-19 - 13:23
In the family of
metallocenes, MgCp*2 (Cp* = pentamethylcyclopentadienyl)
exhibits a regular linear sandwich structure, whereas CaCp*2 is bent in both the gas phase and solid state. Bending is typically
observed for metal ions which possess a lone pair. Here, we investigate
which electronic differences cause the bending in complexes lacking
lone pairs at the metal atoms. The bent gas-phase geometry of CaCp*2 suggests that the bending must have an intramolecular origin. Geometry optimizations with and without dispersion effects/d-type
polarization functions on MCp2 and MCp*2 gas-phase
complexes (M = Ca, Mg) establish that attractive methyl···methyl
London dispersion interactions play a decisive role in the bending
in CaCp*2. A sufficient polarizability of the metal to
produce a shallow bending potential energy curve is a prerequisite
but is not the reason for the bending. Concomitant ligand-induced
charge concentrations and localizations at the metal atoms are studied
in further detail, for which real-space bonding and orbital-based
descriptors are used. Low-temperature crystal structures of MgCp*2 and CaCp*2 were determined which facilitated the
identification and characterization of intermolecular pseudo-pregostic interactions, C–H···Ca, in
the CaCp*2 crystal structure.
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Pal, Rumpa; Mebs, Stefan; Shi, Ming W.; Jayatilaka, Dylan; Krzeszczakowska, Joanna M.; Malaspina, Lorraine A.; et al. (2018). Linear MgCp*2 vs Bent CaCp*2: London Dispersion, Ligand-Induced
Charge Localizations, and Pseudo-Pregostic C–H···Ca
Interactions. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.7b03079
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AUTHORS (12)
RP
Rumpa Pal
SM
Stefan Mebs
MS
Ming W. Shi
DJ
Dylan Jayatilaka
JK
Joanna M. Krzeszczakowska
LM
Lorraine A. Malaspina
MW
Michal Wiecko
PL
Peter Luger
MH
Malte Hesse
YC
Yu-Sheng Chen
JB
Jens Beckmann
SG
Simon Grabowsky