year, the second-generation Hoveyda–Grubbs catalyst was described in nearly simultaneous publications by the Blechert and Hoveyda laboratories. Siegfried Blechert's name is not commonly included in the eponymous catalyst name. The Hoveyda–Grubbs catalysts, while more expensive and slower to initiate than the Grubbs catalyst from which they are derived, are popular because of their improved stability. By changing the steric and electronic properties of the chelate, the initiation rate of the catalyst can be modulated, such as in the Zhan catalysts. Hoveyda–Grubbs catalysts are easily formed from the corresponding Grubbs catalyst by the addition of the chelating ligand and the use of a phosphine scavenger like copper(I) chloride: The second-generation Hoveyda–Grubbs catalysts can also be prepared from the 1st generation Hoveyda–Grubbs catalyst by the addition of the NHC: In one study a water-soluble Grubbs catalyst is prepared by attaching a polyethylene glycol chain to the imidazolidine group. This catalyst is used in the ring-closing metathesis reaction in water of a diene carrying an ammonium salt group making it water-soluble as well. Third-generation Grubbs catalyst (fast-initiating catalysts) The rate of the Grubbs catalyst can be altered by replacing the phosphine ligand with more labile pyridine ligands. By using 3-bromopyridine the initiation rate is increased more than a millionfold. Both pyridine and 3-bromopyridine are commonly used, with the bromo- version 4.8 times more labile resulting in even faster rates. The catalyst is traditionally isolated as a two pyridine complex, however one pyridine is lost upon dissolving and reversibly inhibits the ruthenium center throughout any chemical reaction. The principal application of the fast-initiating catalysts is as initiators for ring opening metathesis polymerisation (ROMP). Because of their usefulness in ROMP these catalysts are sometimes referred to as the 3rd generation Grubbs catalysts. The high ratio of the rate of initiation to the rate of propagation makes these catalysts useful in living polymerization, yielding polymers with low polydispersity. Applications Grubbs catalysts are of interest for olefin metathesis. It is mainly applied to fine chemical synthesis. Large-scale commercial applications of olefin metathesis almost always employ heterogeneous catalysts or ill-defined systems based on ruthenium trichloride. References Organoruthenium compounds Catalysts Phosphine complexes Chloro complexes D Substances discovered in the 1990s Ruthenium(II) compounds Cyclohexyl compounds