Using "PtCl4" as the Pt(IV) component in the mixture of aqueous chloroPt(II)/chloroPt(IV) compounds makes the "Shilov" functionalization of alkyl groups considerably faster and more chemoselective to alcohols, and adding hydrogen peroxide re-oxidizes the Pt(II) reduction product to Pt(IV). Run in this manner, the reaction system is long-lived and catalytic in platinum. (C) 2002 Elsevier Science B.V. All rights reserved.