Iridium reactivity

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

A technologically important effect of the lanthanide contraction is the high density of the Period 6 elements (Fig. 16.5). The atomic radii of these elements are comparable to those of the Period 5 elements, but their atomic masses are about twice as large so more mass is packed into the same volume. A block of iridium, for example, contains about as many atoms as a block of rhodium of the same volume. However, each iridium atom is nearly twice as heavy as a rhodium atom, and so the density of the sample is nearly twice as great. In fact, iridium is one of the two densest elements its neighbor osmium is the other. Another effect of the contraction is the low reactivity—the nobility —of gold and platinum. Because their valence electrons are relatively close to the nucleus, they are tightly bound and not readily available for chemical reactions. 

Reactivity studies of organic ligands with mixed-metal clusters have been utilized in an attempt to shed light on the fundamental steps that occur in heterogeneous catalysis (Table VIII), although the correspondence between cluster chemistry and surface-adsorbate interactions is often poor. While some of these studies have been mentioned in Section ll.D., it is useful to revisit them in the context of the catalytic process for which they are models. Shapley and co-workers have examined the solution chemistry of tungsten-iridium clusters in an effort to understand hydrogenolysis of butane. The reaction of excess diphenylacetylene with... 

The chemistry of organorhodium and -iridium porphyrin derivatives will be addressed in a separate section. Much of the exciting chemistry of rhodium (and iridium) porphyrins centers around the reactivity of the M(ll) dimers. M(Por) 2-and the M(III) hydrides, M(Por)H. Neither of these species has a counterpart in cobalt porphyrin chemistry, where the Co(ll) porphyrin complex Co(Por) exists as a monomer, and the hydride Co(Por)H has been implicated but never directly observed. This is still the case, although recent developments are providing firmer evidence for the existence of Co(Por)H as a likely intermediate in a variety of reactions. 

Okada, M., Ogura, S., Dino, W.A., Wilde, M., Flikutani, K. and Kasai, T. (2005) Reactivity of gold thin films grown on iridium Hydrogen dissociation. Applied Catalysis A General, 291, 55-61. 

In the absence of cyclohexene the same procedure yields larger (Ir(0) 9oo) nanoclusters (size 3 0.4nm). Besides zerovalent Iridium- [167,288,290], Rh(0)-nanocluster of the Finke-type have been prepared [290-292]. Finke s nanoclusters have been carefully examined using a combination of modern instrumental analysis methods [167]. It was revealed that the lr(0) core is uncharged and that the iridium particles exhibit an extremely clean, fully exposed, and chemically very reactive metallic surface. 

The reactivity of hydrido(ethoxo) complex 4 was examined (Scheme 6-15) [8]. Metatheses similar to those postulated for alcohol exchange (Eq. 6.5) occurred between HCl, LiCl, phenyl acetate or primary amines and yielded complexes 94. The reaction of 4 with cyclic anhydrides proceeded similarly to give iridium-assisted ring opening products 95. Heterocumulenes afforded the inserhon products 96 into the Ir-O bond. 

Schemes 6-15 Reactivity of hydrido(ethoxo)iridium compiex4...

The reactivities of several hydrido(carboxylato) complexes of iridium have been studied [58]. Complexes 88 reacted with carbon monoxide to afford carbonyl complexes, [IrCl(H)(OCOR)(CO)(PPh3)2] (98), in which the carboxylato ligands changed to monodentate ligands and exist as a mixture of isomers (Eq. 6.31). 

An alternative route for stabilization of quinone methides by metal coordination involves deprotonation of a ri5-coordinated oxo-dienyl ligand. This approach was introduced by Amouri and coworkers, who showed that treatment of the [Cp Ir(oxo-ri5-dienyl)]+ B1, 22 with a base (i-BuOK was the most effective) resulted in formation of stable Cp Ir(r 4-o-QM) complexes 23 (Scheme 3.14).25 Using the same approach, a series of r 4-o-QM complexes of rhodium was prepared (Scheme 3.14)26 Structural data of these complexes and a comparison of their reactivity indicated that the o-QM ligand is more stabilized by iridium than by rhodium. 

The coordinated quinone methide Jt-system of complex 24 can also undergo cycloaddition (Scheme 3.17). When 24 was reacted with /V-methylmaleimide, a [3+2] cycloaddition took place to give the tricyclic iridium complex 29. The closest example to this unprecedented reactivity pattern is a formal [3 + 2] cycloaddition of /)-quinone methides with alkenes catalyzed by Lewis acids, although in that reaction the QMs serve as electron-poor reagents. 36... 

Interest in the synthesis and reactivity of coordinatively unsaturated low-valent metal complexes has led to the use of an o-carboranedithiolato ligand in the formation of metalladithiolene ring complexes. Recently, we69 70 and Wrackmeyer et al.1 72 have reported on the synthesis of the 16e cobalt, rhodium, and iridium... 

The insertion reactivity of the electrophilic iridium methylene species 57 was noted above. A cationic iridium methylene complex is also the likely intermediate in the thermal rearrangement of Ir(=CH2)I(CO)(PPh3)2 to the ortho-metallated ylide complex 75 ([Pg.167]

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