A series of phosphines with different heterocycles (pyridine and imidazole) possessing different substituents (alkyl and aryl) were synthesized. The phosphine ligands were reacted with different metal precursors to from organometallic complexes which were applied to catalysis. This dissertation describes, part of the discovery process of a uniquely active and selective catalyst for alkene isomerization and the importance of heterocyclic ring in the ligand, enhancing the acceleration of the reaction to almost 11,000 times faster than a non-heterocyclic analog. Further investigation of the isomerization catalyst, as a catalyst for cycloisomerization of alkynols led to discovery of the fact that a related alkyne hydration catalyst, reported by Dan Lev in 2004, was broadly useful in cycloisomerization reactions leading to synthesis of both indoles and benzofurans. A series of allylpalladium(II) chloride bifunctional phosphine complexes were also synthesized and characterized and eventually applied as catalysts for aryl amination reactions. Finally, two mechanistically distinct approaches to anti-Markovnikov alkene hydration using bifunctional ligands are described, which show promise for further development.