[1] This explains why the early transition metals, whose electronegativities and effective nuclear charges are low, are very oxophilic.
For example, the high valent chlorides hydrolyze rapidly to give oxides: These reactions proceed via oxychloride intermediates.
Typically the oxide-ligand is bridging, e.g. Only in rare cases do the products of oxygenation feature terminal oxo ligands.
[2] Oxophilic reagents are often used to extract or exchange oxygen centers in organic substrates, especially carbonyls (esters, ketones, amides) and epoxides.
The highly oxophilic reagent generated from tungsten hexachloride and butyl lithium is useful for the deoxygenation of epoxides.