Tris iridium complex

Reaction of the cyclopentadienyl rhodium and iridium tris(acetone) complexes with indole leads to the species 118 (M = Rh, Ir) [77JCS(D)1654 79JCS(D)1531]. None of these compounds deprotonates easily in acetone, but the iridium complex loses a proton in reaction with bases (Na2C03 in water, r-BuOK in acetone) to form the ri -indolyl complex 119. This reaction is easily reversed in the presence of small amounts of trifluoroacetic acid. 

In the rhodium and iridium complexes, the C-coordination, carbene function, and cyclometallated cases prevail. Benzothiazole-2-thione was studied extensively as a ligand and various situations of the exocyclic S-monodentate coordination as well as N,S-combinations in the di-, tri-, and tetranuclear species were discovered. 

The first iridium complex used in PHOLED devices was fac tris(2-phenylpyridine) iridium Ir(ppy)3 complex [282]. It has a short triplet lifetime ( 1 ps) and high phosphorescent efficiency (p = 40% at room temperature in solution) [283]. However, in the solid state, most iridium complexes showed very low phosphorescent QE due to aggregate quenching. In most cases, the complexes have to be diluted in host materials to avoid reducing the... 

Another efficient material introduced by the same group is the green emitting /ac-tris(2-phenylpyridine)iridium [Ir(ppy)3, 67] [38], A suitable host for this phosphorescent emitter is CBP (10). The triplet lifetime is rather short, the experimentally determined value being 500 ns in the CBP matrix. Another iridium complex was shown to emit in the red with high efficiency due to the short phosphorescence lifetime in comparison with PtOEP [165]. 

During a discussion with G Pannetier (Universite Paris VI) in Paris, he mentioned that he thought he had seen evidence for mixed pyridine-phosphine derivatives of the type [(cod)Rh(PPh3)(C5H5N)]BF4 in the Rh series. On returning to Gif, I confirmed this result by isolating the compound and mentioned it to Morris, who tried to obtain the iridium complex. Our initial idea was that a 1 1 phosphine to metal catalyst might be even more active than the 2 1 species. 

The direct borylation of arenes was catalyzed by iridium complexes [61-63]. Iridium complex generated from [lrCl(cod)]2 and 2,2 -bipyridine (bpy) showed the high catalytic activity of the reaction of bis (pinaco la to) diboron (B2Pin2) 138 with benzene 139 to afford phenylborane 140 (Equation 10.36) [61]. Various arenes and heteroarenes are allowed to react with B2Pin2 and pinacolborane (HBpin) in the presence of [lrCl(cod)]2/bipyridne or [lr(OMe)(cod)]2/bipyridine to produce corresponding aryl- and heteroarylboron compounds [62]. The reaction is considered to proceed via the formation of a tris(boryl)iridium(lll) species and its oxidative addition to an aromahc C—H bond. 

With the knowledge that 14 can activate aldehydes in 1, the role of 1 in the reaction was explored further. Specifically, the relative rates of C—H bond activation and guest ejection, and the possibility of ion association with 1, were investigated. The hydrophobic nature of 14 could allow for ion association on the exterior of 1, which would be both cn t h al pi cal I y favorable due to the cation-it interaction, and entropically favorable due to the partial desolvation of 14. To explore these questions, 14 was irreversibly trapped in solution by a large phosphine, which coordinates to the iridium complex and thereby inhibits encapsulation. Two different trapping phosphines were used. The first, triphenylphosphine tris-sulfonate sodium salt (TPPTS), is a trianionic water-soluble phosphine and should not be able to approach the highly anionic 1, thereby only trapping the iridium complex that has diffused away from 1. The second phosphine, l,3,5-triaza-7-phosphaadamantane (PTA), is a water-soluble neutral phosphine that should be able to intercept an ion-associated iridium complex. 

Iridium complexes with O-donor ligand environments, Ir(triso)(ol)2 [triso = tris(diphenyloxophosphoranyl)methanide ol = C2H4, cyclooc-tene), catalyze the hydrosilylation and dehydrogenative silylation of ethylene with triphenylsilane.35 Diphenylmethylsilane can also be used in the... 

The X-ray structure of 170 has been reported (56). Generally only unsubstituted sp -hybridized carbon atoms of butadiene ligands are attacked by HFA (133). Different behavior has been found in the reactions of iridium complexes with HFA. With tris(triphenylphosphane)nitrosyliridium the geometry is retained [Eq. (139)] (63). However, the Vaska complexes lead to... 

Three iridium complexes of formula [Ir(acac)(L)2] have been synthesized, [k(dpp)2 (acac)], [Ir(bpp)2(acac)j and [Ir(fpp)2(acac)j, where L is a substituted arylpyridine (dpp = 2,4-diphenylpyridine bpp = 2-(4-f-butylphenyl)-4-phenylpyridine fpp = 2-(4-fluoroph-enyl)-4-phenylpyridine). The OLEDs based on these materials, with structure ito/Ir com-plexipvk/F-tbb/Alqs/LiF/Al (F-tbb = l,3,5-tris(4-fiuorobiphenyl-4 -yl)benzene), showed maximum luminances of 8776, 8838 and 14180 cdm , and maximum external efficiencies of 11.5, 12.9 and 17.0 cdA, repectively ° . 

A successful study of non-phosphine iridium complexes Ir", Ir , and Ir e. g., IrX(cod)2 [60], IrH2(triso)(SiMePh2)2 [61, 62], Ir(triso)(coe)2 (coe = cyclooctene triso = tris(diphenyloxophosphoranyl)methanide), Ir(triso)(C2H4)2 [61], has demonstrated effective hydrosilylation of alkenes and alkynes. Iridium phosphine complexes, e. g., Ir(C=CPh)(CO)2PCy2 [63] and IrCl(CO)(PPh3)2 [64], are also found to be active for hydrosilylation of phenylacetylene and 1-hexyne. 

From a coordination point of view, Complex 75 and the related ruthenium complex [(ij6-p-cymene)Ru(pz)2(Hpz)], 76 (7), are comparable to protonated polypyrazolylborates RB(pz)2(pzH) (R = H or pz) (12). The formal similarity between the tris(pyrazolyl)borate anion and the deprotonated form of the iridium complex 75 suggested the preparation of heterodinuclear complexes by using 75 as a building block. Thus, heterodinuclear (n-pz)2 complexes of the formula [(C5Me5)(pz)Ir(/i-pz)2M(PPh3)] (M = Cu, 77 Ag, 78 Au, 79) were obtained (96). 

BINAP complexes have been used extensively in asymmetric synthesis, for example in hydrogenations,389,390 olefin isomerizations,390 arylation of olefins,391 and enantioselective allylation of aldehydes.392 Palladium or platinum complexes of (165) find important applications in enantioselective C—C bond formation,393-396 whilst iridium complexes are catalysts for the hydrogenation of nonfunctionalized tri- and tetrasubstituted olefins. 97... 

One of the first detailed studies of OA was performed by L. Vaska57 on 16-electron square planar iridium complexes, the most notable of which is currently known as Vaska s compound, the central compound in Scheme 7,3. The reactions portrayed in Scheme 7.3 indicate that several different kinds of molecules react with the iridium complex. Mechanistic pathways leading to the products shown and to products resulting from other metal complexes are many and varied. We will consider a few of these mechanistic types, trying to point out as we go along similarities to other reactions from the realm of organic chemistry. 

In 2008, Vries group reported asymmetric hydrogenation of quinolines catalyzed by iridium complexes based on monodentate BINOL derived phos phoramidites PipPhos. They used tri ortho tolylphosphine and/or chloride salts as additives, and enantioselectivities were strongly enhanced to 89% ee (Scheme 10.13) [17]. Toluene and DCM were the best solvents, and the reaction was carried out at 60°C for 24h in the pressure of 50 bar H2, and a series of 2 substituted and 2,6 disubstituted quinolines were examined with excellent... 

---