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Alkaline Earth Metal

The document discusses the chemistry of Group 2 elements, including their bonding properties and molecular structures. It examines the bent structures of heavier Group 2 element dihalides and explains this in terms of inverse polarization and participation of d orbitals. It also discusses the structures of beryllocene in the gas phase and crystal state.

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mandalsuman20092001
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40 views49 pages

Alkaline Earth Metal

The document discusses the chemistry of Group 2 elements, including their bonding properties and molecular structures. It examines the bent structures of heavier Group 2 element dihalides and explains this in terms of inverse polarization and participation of d orbitals. It also discusses the structures of beryllocene in the gas phase and crystal state.

Uploaded by

mandalsuman20092001
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Chemistry of Group 2 Elements

(Alkaline Earth Metals along with the chemistry of Group 12)


In the Gas Phase Bond Angles
The most bent of the dihalides is BaF . It has a bond angle in the region
2

of 110–126 (values come from a range of theoretical and experimental


data) and the calculated energy to convert bent BaF to a linear molecule
2

is ~21 kJ mol.

The preference for bent structures for the heaviest metals combined
with F, Cl or Br has been explained in terms of both ‘inverse (or core)
polarization’ and the participation of d atomic orbitals for Ca, Sr and Ba.

Inverse polarization occurs when the metal ion is polarizable and is


polarized by F- or Cl-. The polarization is termed ‘inverse’ to distinguish it
from the polarization of a large, polarizable anion by a cation.
An alternative explanation: Participation of d orbitals in the bonding.

Be and Mg form only linear gaseous dihalides. These two metals have only
s and p atomic orbitals available for bonding and the best M-X orbital
overlap is achieved for a linear molecule.

For Ca, Sr and Ba, vacant 3d, 4d and 5d orbitals, respectively, are available,
but can only overlap efficiently with orbitals on the X atoms if the MX2
molecule is bent. Two interactions must be considered as shown in
diagram (the axes are defined arbitrarily as shown).

The out-of-phase combination of X– – –X orbitals only overlaps efficiently


with the dyz orbital of M if the MX2 molecule is bent; opening the
molecule up to a linear shape ‘switches off’ this orbital interaction.
Although the interaction between the metal dz2 orbital and the in-phase
combination of X– – –X orbitals is most efficient when MX2 is linear, it is
still effective when the molecule is bent.
Gas phase Crystal
Cp2Be
A low-temperature X-ray crystal-structure analysis (Beattie, 1984) clarified the
situation. The results showed that crystalline beryllocene adopts a slipped
sandwich structure in which the two Cp rings are staggered, corresponding to the
formulation (η1-C5H5)(η5-C5H5)Be. The dashed lines in the figure indicate that the
Be atom can occupy two equivalent positions between the staggered rings; in the
crystal, the positions are occupied statistically.

A reinterpretation of the electron-diffraction data also leads


to this type of structure for gaseous beryllocene.
A Fluoride Grignard!

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