Wednesday, October 4, 2017

reactivity - Why are silyl chlorides more readily hydrolysed than alkyl chlorides?


I know that the $\ce{Si-Cl}$ bond has a slightly higher energy, but silyl chlorides are much more readily hydrolyzed compared to alkyl chlorides. I do not fully understand why that is. My thoughts so far are:





  • There is a better match in energy between the orbitals of the $\ce{Si-Cl}$ bond and water.




  • Reactions proceed when there is a favorable interaction between HOMO and LUMO.




  • In this case, the HOMO is the lone pair on the water molecule. The LUMO of a $\ce{Si-Cl}$ bond is closer to it in energy compared to a $\ce{C-Cl}$ bond.





Is this the right argument to take?




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periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, $\ce{Mg^2+}$ is closest in radius to $\ce{Li+}$. Is this true, and if so, why would a whole larger shell ($\ce{...