Provided are methods and materials for the functionalization of a heteroalkane or arene using an oxidizing electrophile as a stoichiometric agent or catalyst. The reaction involves the replacement of a hydrogen atom on an sp3-hybridized carbon atom of the heteroalkane or of a hydrogen atom on an sp2-hybridized carbon atom of the arene. A main group element organometallic intermediate is formed that undergoes further conversion to a functionalized heteroalkane or arene.