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This is because the least electronegative element is able to share more electrons when compared to a more electronegative element. This also may be because less electronegative atoms tend to have a lower number of electrons in the valence shell, so it is easier to add more electrons into its valence shell.
I believe that the reason the least electronegative atom is in the center of an atom because the element in the center of the atom have to share electrons with all the other surrounding elements. By having the least electronegative atom in the center allows for a more stable bond between the elements because the center atom will be more prone to share the electrons within a covalent bond. However, the least electronegative atom is not always in the center as H2O has Oxygen in the center of the atom. This is because Hydrogen is only capable of forming one bond and thus could not be the center atom.
Adding on to what others have said about having the least electronegative atom in the middle, I believe I heard Lavelle saying that many of the compounds that are created from the bonds have Hydrogen in them and Hydrogen atoms are nearly always at the very ends of the Lewis structure.
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