Journal of Inorganic and Organometallic Polymers, Vol. 2, No. 3, 1992 Functionalization of Halogenated Polystyrene Resins Utilizing Highly Reactive Calcium Richard A. O'Brien, 1 Tian-an Chen, 1 and Reuben D. Rieke 1"2 Received June 13, 1991; revised September 3, 1991 Polymeric organocalcium reagents were prepared via the oxidative addition of highly reactive calcium, prepared from the lithium biphenylide reduction of calcium iodide, to cross-linked p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, and chloromethylatedpolystyrene.These organocalcium reagents react with a variety of electrophiles to yield functionalizedpolymers. KEY WORDS: Functionalization; polymers; highly reactive calcium; p-bromopolystyrene,chloromethylated polystyrene; organocatciumreagent. INTRODUCTION Chemical modification of cross-linked polystyrene resins has received considerable attention in the literature and these resins have important applications throughout chemistry [1 ]. Transformations are normally only possible with a soluble reagent interacting in an intimate fashion with the insoluble polymer. Recently, the formation of polymers containing Grignard reagents was reported by Fr6chet et al. [2a, 2c] and Harvey and Raston [2b] in which the soluble reagent, magnesium anthracene, reacted with insoluble polymers containing chloromethyl groups or aryl and alkyt bromides. The direct oxidative addition of highly reactive copper with cross-linked p-bromopolystyrene with varying degrees of bromination was recently reported by our group [3]. In this communication, we report the first preparation of organocalcium reagents by the addition of highly reactive soluble calcium to halogenated cross-linked polystyrene resins and subsequent reaction with a variety of electrophiles to prepare functionalized insoluble polymers. The development of organocalcium 1Department of Chemistry, Universityof Nebraska-Lincoln, Lincoln, Nebraska 68588-0304. 2 To whom correspondenceshould be addressed. 345 1053-0495/92/0900-0345506.50/0 © 1992 Plenum Publishing Corporation