Coordination of iridium

A wide range of iridium complexes are formed in the -1-3 oxidation state, the most important for iridium, with a variety of ligands. The vast majority have octahedral coordination of iridium. 

Presumably, the stereoselectivity in these cases is the result of coordination of iridium by the functional group. The crucial property required for a catalyst to be stereodirective is that it be able to coordinate with both the directive group and the double bond and still accommodate the metal hydride bonds necessary for hydrogenation. In the iridium catalyst illustrated above, the cyclooctadiene ligand (COD) in the catalysts is released by hydrogenation, permitting coordination of the reactant and reaction with hydrogen. 

The most common oxidation states, corresponding electronic configurations, and coordination geometries of iridium are +1 (t5 ) usually square plane although some five-coordinate complexes are known, and +3 (t7 ) and +4 (t5 ), both octahedral. Compounds ia every oxidation state between —1 and +6 (<5 ) are known. Iridium compounds are used primarily to model more active rhodium catalysts. 

Organometallic chemistry of pyrrole is characterized by a delicate balance of the ti N)- and -coordination modes. Azacymantrene is an illustration of the considerable nucleophilicity of the heteroatom. However, azaferrocene can be alkylated at C2 and C3 sites. Ruthenium and osmium, rhodium, and iridium chemistry revealed the bridging function of pyrroles, including zwitterionic and pyrrolyne complex formation. The ti (CC) coordination of osmium(2- -) allows versatile derivatizations of the heteroring. 

In synthesis (b), the initial product is a 5-coordinate (sp) iridium(III) hydride complex, which is rapidly oxidized in solution to the planar iridium(II) complex. Both of the compounds are paramagnetic with one unpaired electron, as expected for square planar d7 complexes. 

A considerable number of the tertiary phosphine and arsine complexes of iridium(III) have been synthesized [4, 8] they generally contain 6-coordinate iridium and are conventionally prepared by refluxing Na2IrCl6 with the phosphine in ethanol or 2-methoxyethanol [154]... 

Two other publications on Ir (73 keV) Mossbauer spectroscopy of complex compounds of iridium have been reported by Williams et al. [291,292]. In their first article [291], they have shown that the additive model suggested by Bancroft [293] does not account satisfactorily for the partial isomer shift and partial quadrupole splitting in Ir(lll) complexes. Their second article [292] deals with four-coordinate formally lr(l) complexes. They observed, like other authors on similar low-valent iridium compounds [284], only small differences in the isomer shifts, which they attributed to the interaction between the metal-ligand bonds leading to compensation effects. Their interpretation is supported by changes in the NMR data of the phosphine ligands and in the frequency of the carbonyl stretching vibration. 

The coordination chemistry of iridium has continued to flourish since 1985/86. All common donor atoms can be found bound to at least one oxidation state of iridium. The most common oxidation states exhibited by iridium complexes are I and III, although examples of all oxidation states from —I to VI have been synthesized and characterized. Low-oxidation-state iridium species usually contain CO ligands or P donor atoms, whereas high-oxidation-number-containing coordination compounds are predominantly hexahalide ones. 

The most common use of iridium coordination compounds remains in the catalysis field, although interest is developing in the luminescent properties of iridium compounds. The wide range of accessible oxidation states available to iridium (—1) to (VI) is reflected in the diverse nature of its coordination compounds. 

The functional form of this rate expression is consistent with the behavior of the iridium system observed throughout the kinetic investigations. The coordination of nitrile to iridium is anticipated to produce more than a simple inhibitory effect. Being the dominant equilibrium in the mechanism, nitrile coordination may produce the observed first order dependence of the reaction rate with respect to hydrogen. Given Kcn[RCN] is the predominant term in the denominator, the rate expression may be reduced to the form of (8) which is first order with respect to both olefin and [H2]. 

Successive hydrogen transfers within 60, followed by coordination of olefin and then H2 (an unsaturate route), constitute the catalytic cycle, while isomerization is effected through HFe(CO)3(7r-allyl) formed from 59. Loss of H2 from 60 was also considered to be photoinduced, and several hydrides, including neutral and cationic dihydrides of iridium(III) (385, 450, 451), ruthenium(II) (452) and a bis(7j-cyclopentadienyltungsten) dihydride (453), have been shown to undergo such reductive elimination of hydrogen. Photoassisted oxidative addition of H2 has also been dem-... 

Structural studies on the nature of the organometallic intermediates following chelation-assisted CH additions of pincer iridium complexes have been carried out. The product was found to have an unexpected /ram-disposition of the hydride with respect to the metallated aromatic group. This is not the expected direct outcome of a chelation-assisted reaction since coordination of oxygen to iridium prior to C-H activation would be expected to afford the m-isorner (Equation (97)). 

The mechanistic basis of iridium-complex-catalyzed enantioselective hydrogenation is less secure than in the rhodium case. It is well known that square-planar iridium complexes exhibit a stronger affinity for dihydrogen than their rhodium counterparts. In earlier studies, Crabtree et al. investigated the addition of H2 to their complex and observed two stereoisomeric intermediate dihydrides in the hydrogenation of the coordinated cycloocta-1,5-diene. The observations were in contrast to the course of H2 addition to Ms-phosphine iridium complexes [69]. 

A remarkable feature of iridium enantioselective hydrogenation is the promotion of the reaction by large non-coordinating anions [73]. This has been the subject of considerable activity (anticipated in an earlier study by Osborn and coworkers) on the effects of the counterion in Rh enantioselective hydrogenation [74]. The iridium chemistry was motivated by initial synthetic limitations. With PFg as counterion to the ligated Ir cation, the reaction ceases after a limited number of turnovers because of catalyst deactivation. The mechanism of... 

Surface Organometallic and Coordination Chemistry of Iridium, Platinum, and Gold Electrocatalysts... 

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