The formation and breaking of covalent bonds is a fundamental aspect of chemistry. Typical reactions with olefins form or break a bond to produce a desired transformation in an irreversible process in order to drive the reaction to completion. The idea of temporary bonding to activate olefins is a common topic in catalysis, but usually does not result in fully covalent character. Since the advent of organocatalysis, the idea of temporarily and reversibly forming covalent bonds has seen rapid development. The Lambert group has studied organocatalysis for use in both small molecule transformations and more recently polymerization.This dissertation will discuss two projects revolving around the formation and breakage of a covalent bond to an olefin: (1) pentacarboxyclcylopentadiene (PCCP) catalysts for controlled cationic polymerization of vinyl monomers and (2) the separation of olefins and paraffins by chemiselective olefin capture and release. Chapter 1 provides an introduction to cationic polymerization of vinyl monomers, the background and use of PCCP catalysts in polymerization, and previous derivatives of PCCPs. Following is an exploration of various derivatives of PCCPs for the polymerization of vinyl ethers and expansion of the monomer scope to styrenes is detailed. In particular, the use of alkylated PCCP catalysts enabling the polymerization of p-methylstyrene by reversible ionization of a covalent C-C bond is presented for the first time. Chapter 2 discusses the importance of olefin-paraffin separation and the background of nitrone cycloaddition chemistry. A brief investigation of this reactions use in the capture and release of olefins is discussed. This chapter also provides the motivations for the development of the following chapter. Chapter 3 introduces the chemistry of sulfenic acids and their application to olefin capture. The development of a solution phase method of olefin addition to sulfenic acid then elimination from the resulting sulfoxide in a cyclable manner is detailed. Using this reaction system as a proof of concept, attempts at designing a rigid porous material functionalized with sulfenic acid for more efficient gas phase separation are discussed.