CARBONYLS, PHOSPHINE COMPLEXES, AND LIGAND SUBSTITUTION REACTIONS

CARBONYLS, PHOSPHINE COMPLEXES, AND LIGAND SUBSTITUTION REACTIONS 

In this chapter, we first examine how CO, phosphines, and related species act as ligands, then look at ways in which one ligand can replace another by 

This has been studied in most detail for the case of the substitution of CO groups in metal carbonyls by a variety of other ligands, such as tertiary phosphines, PR3. The principles involved will be important later, for example, in catalysis. 

---

Support-bound transition metal complexes have mainly been prepared as insoluble catalysts. Table 4.1 lists representative examples of such polymer-bound complexes. Polystyrene-bound molybdenum carbonyl complexes have been prepared for the study of ligand substitution reactions and oxidative eliminations [51], Moreover, well-defined molybdenum, rhodium, and iridium phosphine complexes have been prepared on copolymers of PEG and silica [52]. Several reviews have covered the preparation and application of support-bound reagents, including transition metal complexes [53-59]. Examples of the preparation and uses of organomercury and organo-zinc compounds are discussed in Section 4.1. 

Ruthenium(IT), d A wide range of Ru complexes incorporating carbonyl, phosphine, ammine and heterocyclic ligands are known. Virtually all Ru complexes are octahedral and diamagnetic with a l2g configuration (unless steric constraints are present). Catalytic processes utilizing Ru" phosphine complexes, kinetic studies on substitution reactions of [Ru(NH3)5L] " and the photophysics and photochemistry of [Ru(bipy)j] and related systems have been areas of major advance in recent years. 

Several other recent reviews contain material relevant to this section. An article by Blandamer and Burgess on the thermodynamics, kinetics, and mechanisms of solvation, solvolysis, and substitution in nonaqueous solvents contains a contribution on the controversial dissociative mechanism for isomerization of square-planar molecules. This is outlined in Section 5.5. A review of ligand substitution reactions at low-valency transition-metal centers contains sections on five-coordinate metal carbonyl complexes and on ML4 complexes (mainly tetrahedral configurations with L being a tertiary phosphine), as well as on acid- and base-catalyzed reactions. A review by Constable " surveying the reactions of nucleophiles with complexes of chelating heterocyclic imines contains a sizable section on square-planar palladium and platinum derivatives. Most discussion centers on [Pt(bipy)2] and [Pt(phen)2] (bipy = 2,2 -bipyridine phen = 1,10-phenanthroline). The metal center, ligand, or both are susceptible to nucleophilic attack and the mechanisms involved are critically assessed. 

Mononuclear acyl Co carbonyl complexes ROC(0)Co(CO)4 result from reaction of Co2(CO)8 with RO-.77 These also form via the carbonylation of the alkyl precursor. The ROC(0)Co(CO)4 species undergo a range of reactions, including CO ligand substitution (by phosphines, for example), decarbonylation to the alkyl species, isomerization, and reactions of the coordinated acyl group involving either nucleophilic attack at the C or electrophilic attack at the O atom. 

Substituted cyclopentadienones react with iron carbonyls to form stable, diamagnetic 7r-co triplexes of the type [Fe(CO)3(cyclopentadienone)] (215). The proposed structure is shown in (XX). These complexes undergo reactions typical of metal carbonyls, e.g., displacement of carbon monoxide by tertiary phosphines, but the carbonyl group of the ligand does not show reactions characteristic of a keto-group. These complexes are also formed by interaction of acetylenes with iron carbonyls (see Section VI,C). Interaction of tetracyclone and Fe3(CO)i2 gives unstable complexes which contain the sandwich anion [Fe(tetracyclone)2]2 analogous to the anion (XXV) (215). 

---