Coordination Complexes as Catalysts

Coordination Complexes as Catalysts The first half of the book focuses on the use of coordination complexes as catalysts for a diverse range of organic reactions. Chapters on supported metal complexes and combinatorial catalysis are also included in this half of the book. Chapter 1, covering catalysts for polymerisation, is not an area where platinum group metal (pgm) complexes would be expected to dominate. There is, however, an interesting section on the reemergence of Ru initiators for polymerisation. The use of Ru complexes (some now commercially available) for ring opening metathesis polymerisation (ROMP) of cyclic alkenes is discussed. Chapter 2 by C. Pettinari, F. Marchetti and D. Martini covers metal complexes as hydrogenation catalysts with, naturally, a heavy emphasis on enantioselective reactions. I liked this chapter with its focus on mechanism and careful choice of example to demonstrate each point. Work which has become of industrial importance is covered together with proper discussion of Noyori’s ground breaking design and synthesis of RuCl2(diphosphine)(1,2-diamine) catalysts. The second half of the chapter concentrates on new developments and covers hydrogenation and enantioselective hydrogenation in aqueous systems and in supercritical CO2, and biphasic catalysis amongst other topics. Additionally hydrogenation by Os and Ru cluster complexes is also discussed. Metal complexes as catalysts for the addition of carbon monoxide is the focus of Chapter 3. This is obviously a huge area and the authors (P. W. N. M. van Leeuwen and C. Claver) have concentrated on work which explicitly uses coordination complexes rather than materials prepared in situ. Additionally they cite a large number of review articles. The chapter begins by discussing the BP Cativa process (2) where Ir has found advantage over Rh for the carbonylation of methanol. A large section on hydroformylation covers PtSnCl2/phosphines as well as the extensive Rh chemistry dominated by phosphine or phosphite ligand systems. Drent’s work with Pd is also included. Asymmetric hydroformylation with these types of systems is dealt with in separate sections. The development of thermoplastics has required the copolymerisation of alkenes and carbon monoxide; and the use of Pd complexes with chelating bidentate phosphine ligands, amongst others, is surveyed. The chapter concludes with sections on reductive carbonylation of nitro groups and the use of Pd complexes for hydroxyand methoxycarbonylation. In Chapter 4, T. Katsuki discusses metal complexes as catalysts for oxygen-, nitrogenand carbon-atom transfer to alkenes. Ru metalloporphyrin and metallosalene complexes feature as catalysts for chiral epoxidation and mention is made of work where molecular oxygen is the oxidant. Ru salen complexes have been found to be efficient catalysts for aziridination. Os chemistry dominates the section on dihydroxylation. In particular complexes with diamine and bis-cinchona ligands have excellent enantioselectivity. The Sharpless and Carey mechanistic models are thoroughly covered. There is a large section on the use of Rh and Ru catalysts for interand intramolecular cyclopropanation. The addition of H-X (X = B, CN, Si, N and P) to carbon-carbon multiple bonds is reviewed by M. K. Whittlesey in Chapter 5. The comprehensive section on hydroboration covers a lot of work with Applications of Coordination Complexes