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Updated: Nov 2, 2025
Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique
Published on: November 3, 2017
Bonding in Barium Boryloxides, Siloxides, Phenoxides and Silazides: A Comparison with the Lighter Alkaline Earths
Erwann Le Coz1, Joanna Hammoud1, Thierry Roisnel1
1Univ Rennes, CNRS ISCR, Institut des Sciences Chimiques de Rennes)-UMR 6226, 35000, Rennes, France.
Abstract:
Barium complexes ligated by bulky boryloxides [OBR2 ]- (where R=CH(SiMe3 )2 , 2,4,6-i Pr3 -C6 H2 or 2,4,6-(CF3 )3 -C6 H2 ), siloxide [OSi(SiMe3 )3 ]- , and/or phenoxide [O-2,6-Ph2 -C6 H3 ]- , have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2 -X1 )(X2 )]2 depends largely on the given pair of ligands X1 and X2 . Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3 )2 }2 )]- <[N(SiMe3 )2 ]- <[OSi(SiMe3 )3 ]- <[O(2,6-Ph2 -C6 H3 )]- <[OB(2,4,6-i Pr3 -C6 H2 )2 ]- . This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H-C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ2 -N(SiMe3 )2 }(OB{CH(SiMe3 )2 }2 )]2 (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ2 -X1 )(X2 )]2 heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands.
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