Iridium complexes oxygen

In 1963 Vaska 164) discovered that the iridium complex Ir(PPh3)2C (CO) takes up molecular oxygen reversibly with 1 1 stoichiometry. This complex has since been shown to reversibly sorb (1 1) ethylene (755), carbon dioxide (765), F2C=CF2 and F3C—C=C—CF3 (767), as well as various other ligands (765). Ibers md La Placa (769)... 

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)). 

Alkylation of sp3 C-H bonds adjacent to a heteroatom such as nitrogen and oxygen is possible. The early works using tungsten or iridium complexes involved the reaction of dimethylamine with 1-pentene (Equation (29)) and the alkylation of a C-H bond adjacent to oxygen with / r/-butylethylene.34,34a,34b... 

The isomerization of the (Z)-isomer into the ( )-isomer promoted by the iridium complex explains the lack of stereospecificity of the transformation. O-Alkylated oximes and ketoximes do not react and this fact suggests that the presence of both hydrogen and a hydroxyl group is required for the success of the transformation. The authors proposed that the initial displacement of a chloride ion of the iridium complex by the oxime allows the iridium to remove both the oxygen and the hydride from the initial oxime. Swapping places of both substituents produces the amide. 

These solid-gas reactions represent, at the moment, the single path to 3-metalla -l,2-dioxolane complexes of rhodium and iridium. Complexes of this type have been widely proposed in catalytic cycles. However, it is unlikely that they take part in oxygenations with rhodium because of their high reactivity (see below) and the special conditions for their preparation. 

An X-ray crystal structure of 55, redrawn as Fig. 10, supported the formulation of the complex as that of a peroxo system. Further, the structure demonstrated that no interactions between the [Of-] ligand and the borate moiety were possible because of the relative arrangement of the [Of-] and borate ligands about the iridium center. Such interactions were implicated in the oxygen-initiated decomposition of the iridium complex of 52, while the lack of reactivity of the iridium complexes of 53 and 54 was attributed to steric factors arising from the alkyl chains connecting the sulfur atoms. 

Iridium complexes having oxygen ligands are not nearly as extensive as those having nitrogen. Examples include acetylacetonates [Ir(P(C(5H5)3)2 (acac)H2] [64625-61-2], aqua complexes Ir(OH2)6]3+ [61003-29-0], nitrato complexes [Ir(0N02)(NH3),J2 [42482 42-8], and peroxides IrCl(P(C6I fy)3)2(02-/-(>/ I I9)2(CO) [81624-11-5]. Unlike rhodium, very few Ir(II) carboxylate-bridged dimers have been claimed and [Ir,2(OOCCI I3)4 has not been reported. Some Ir(T) complexes exhibit reversible oxidative addition of 02 to form Ir(III) complexes. That chemistry has been reviewed (172). 

Iridium Complexes. The air-stable, rose-colored monohydride HIrCl2(PCy3)2, Complex 3, may be prepared directly from a commercially available chloride, or by adding HC1 to a toluene solution containing the cyclooctene dimer [IrCl(COT)2]2 and PCy3. The six-coordinate, yellow Complex 4 containing oxygen-bonded dma, v(CO) 1628 cm-1 (28), also is isolated readily. 

In another example, the cyclometalated iridium complex [Ir(ppy)2(4-vinylpyridine)Cl] has been attached via hydrosilation see Hydrosilation) to hydride-terminated poly(dimethylsiloxane) to produce a luminescent material. Evaluation of this material as a luminescent oxygen sensor revealed significantly improved sensitivity over dispersions of the original vinyl pyridine complex in poly(dimethylsiloxane). The luminescent material was blended with polystyrene to give a new sensor that exhibited increased sensitivity and maintained short response times to rapid changes in air pressure. 

Evidence for a radical pathway includes the observation that the reaction is accelerated by radical initiators (such as oxygen or peroxides) and the presence of UV light. Moreover, the order of reactivity for the R group is IIP > II0 > 1°, which is inconsistent with a direct displacement mechanism, but is in accord with the stability of alkyl radicals. Radical inhibitors (such as steri-cally hindered phenols) retard the rate of reaction with sterically-hindered alkyl halides, but not when R = methyl, allyl, and benzyl. When stereoisomerically pure alkyl halides are used, OA results in the formation of a 1 1 mixture of stereoisomeric alkyl iridium complexes, consistent with the formation of an intermediate radical R-. 

Vaska, L. Chen, L. S. Senoff, C. V. Oxygen-carrying iridium complexes kinetics, mechanism, and thermodynamics. Science 1971, 174, 587-589. 

Even oxygen nucleophiles have been introduced with good enantioselectivity using both palladium- and iridium-based catalysts. The conditions of the reaction need to be sufficiently mild that the product does not become a substrate for the allylic substitution, since this will ultimately lead to racemisation. Pivalate ( BuC02 ) and phenols have been used as nucleophiles, in the presence of palladium catalysts, with good results, while linear allylic carbonates are converted into chiral branched products with high ee using phenolates, aUcoxides and also hydroxylamines with iridium complexes. Sulfur nucleophiles have also been used in enantioselective allylic substitution reactions. ... 

Difluoroketene is even more unstable but has been successfully generated in an argon matrix at 7 K by photolysis of difluoroacetylene at 193 nm, forming difluorovinylidene, which led to difluoroketene upon oxygenation by CO2. The ketene was identified by its IR band at 2162 cm f Upon further photolysis it underwent decarbonylation to CF2 (Scheme 7.39). An iridium complex of difluoroketene has also been characterized. 

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