Iridium complexes nitrogen heterocycles

Coordination Compounds. A large number of iridium complexes with nitrogen ligands have been isolated, particularly where Ir is in the +3 oxidation state. Examples of ammine complexes include [Ir(NH3)6]3+ [24669-15-6], [IrCl(NH3)]2+ [295894)9-1], and trans-[Ir(03SCF3)2(en)2]+ [90065-94 4]. Compounds of IV-heterocyclic ligands include trans- [IrCl4(py)2] [24952-67-8], [Ir(bipy)3]3+ [16788-86-6], and an unusual C-metalated bipyridine complex, [Ir(bipy)2(C3,N-bipy)]2+ [87137-18-6]. Isolation of this latter complex produced some confusion regarding the chemical and physical properties of Pi(bipy)3]3+ (167). 

We have already alluded to the diversity of oxidation states, the dominance of oxo chemistry and the cluster carbonyls. Brief mention should be made too of the tendency of osmium (shared also by ruthenium and, to some extent, rhodium and iridium) to form polymeric species, often with oxo, nitrido or carboxylato bridges. Although it does have some activity in homogeneous catalysis (e.g. of m-hydroxylation, hydroxyamination or animation of alkenes, see p. 558, and occasionally for isomerization or hydrogenation of alkenes, see p. 571), osmium complexes are perhaps too substitution-inert for homogeneous catalysis to become a major feature of the chemistry of the element. The spectroscopic properties of some of the substituted heterocyclic nitrogen-donor complexes may yet make osmium an important element for photodissociation energy research. 

Iridium and ruthenium complexes of N-heterocyclic carbenes are particularly sensitive to decomposition by C-H bond activation of the substituents on nitrogen. As described in Section 3.5.2, this reaction can be used productively if reversible. However, it often leads to degradation and loss of catalytic activity. 

---