343978-73-4

Basic information

• Product Name: (2-phenylbenzo[d]oxazole)₂Ir(μ-Cl)₂Ir(2-phenylbenzo[d]oxazole)₂
• Synonyms: (2-phenylbenzo[d]oxazole)₂Ir(μ-Cl)₂Ir(2-phenylbenzo[d]oxazole)₂
• CAS NO: 343978-73-4
• Molecular Weight: 1232.2
• Mol File: 343978-73-4.mol

Chemical Properties

• CAS DataBase Reference: (2-phenylbenzo[d]oxazole)₂Ir(μ-Cl)₂Ir(2-phenylbenzo[d]oxazole)₂(CAS DataBase Reference)
• NIST Chemistry Reference: (2-phenylbenzo[d]oxazole)₂Ir(μ-Cl)₂Ir(2-phenylbenzo[d]oxazole)₂(343978-73-4)
• EPA Substance Registry System: (2-phenylbenzo[d]oxazole)₂Ir(μ-Cl)₂Ir(2-phenylbenzo[d]oxazole)₂(343978-73-4)

Safety Data

• Hazardous Substances Data: 343978-73-4(Hazardous Substances Data)

Upstream product

• 833-50-1 2-phenylbenzo[d]oxazole 

Relevant articles and documents

Color tuning of cyclometalated 2-phenylbenzo[d]oxazole-based iridium(III) complexes through modification of different N^O ancillary ligands

Four new cyclometalated bo-based iridium(III) complexes with different N^O ancillary ligands, [Ir(bo)2pic] (1), [Ir(bo)2prz] (2), [Ir(bo)2bop] (3) and [Ir(bo)2btp] (4) (bo = 2-phenylbenzo[d]oxazole, pic = picolinate, prz = pyrazinate, bop = 2-benzoxazol-2-yl phenol, btp = 2-benzothiazol-2-yl phenol), have been synthesized and investigated by optical spectroscopy, electrochemistry as well as density functional theory (DFT). The crystal structures of 1, 2 and 4 have been determined, which show that each adopts the distorted octahedral coordination geometry. They exhibit intense green to orange phosphorescence (λmax = 531-598 nm) with quantum yields of 0.19-0.94 and lifetimes of 0.078-0.468 μs in solution at 298 K. The broad range color tuning of complexes 1-4 is dependent on the ancillary ligand structure. The cyclic voltammetry has been measured, showing a quasireversible, metal-centered oxidation with potentials at 1.00-1.49 V. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 1-4 have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).

Proline and α-Methylproline as Chiral Auxiliaries for the Synthesis of Enantiopure Bis-Cyclometalated Iridium(III) Complexes

A convenient proline- and α-methylproline-mediated method for the synthesis of enantiomerically pure bis-cyclometalated iridium(III) complexes is reported. The reactions of l-proline or l-α-methylproline with [Ir(μ-Cl)(C^N)2]2(C^N = cyclometalating 2-phenylpyridine, 2-phenylbenzoxazole, or 2-phenylbenzothiazole ligand) afforded diastereomeric mixtures of intermediate prolinatoiridium(III) complexes from which the Λ-(S) diastereomers were isolated with excellent diastereomeric purity by washing, precipitation, or crystallization. A subsequent trifluoroacetic acid (TFA) induced substitution of the prolinate ligands with 2,2′-bipyridine with the retention of configuration provided the chiral-only-at-metal complexes with >99 % ee.

Cyclometalated iridium(III)complexes with ligand effects on the catalytic C-H bond activation of toluene

New cyclometalated iridium(IIcomplexes have been designed, prepared and applied as catalytic systems for the C-H bond activation (CHof toluene through a clean, highly efficient, and environmentally friendly process. The complexes have the general formula [(C^N)2Ir(N^O)]. The C^N ligands are the monoanionic bidentate cyclometalating ligands 2-phenylpyridinato (ppy), 2-phenylbenzoxazolato (pbo), and 2-(3.5-difluorophenyl)-benzoxazolato (dfpbo). The (N^ligand is also a monoanionic bidentate cyclometalating ligand, namely picolinato (pic). The complexes [(ppy)2Ir(pic)] (1), [(pbo)2Ir(pic)] (2), and [(dfpbo)2-Ir(pic)] (3) were structurally characterized by1H and13C NMR spectroscopy, FAB-MS, and X-ray crystallography. The activation energies for the catalytic CHA oxidation of toluene when using complexes 1-3 as catalysts are quite low, between 14.4 and 25.5 kcal mol-1. The catalytic turnover frequencies (TOFare fairly high (up to 4.0 × 103 moltoluene molcatalyst-1 h-1) with excellent reliability and the turnover number (TOcan reach 2.40 × 104 moltoluene molcatalyst-1 after 6 h of reaction time. A combination of catalytic tests, DFT calculations, X-ray absorption nearedge structure (XANEanalysis, and kinetic modeling was used to derive detailed insights into the characteristics of the catalysts and their effect on the reactions featured in the CHA oxidation of toluene.

Cyclometalated Iridium(III) Complexes Containing 2-Phenylbenzo[d]oxazole Ligand: Synthesis, X-ray crystal structures, properties and DFT calculations

Two new iridium(III) complexes were synthesized and fully characterized, [(bo)2Ir(pzpy)] (2a) and [(bo)2Ir(pzpyz)] (2b) (where bo = 2-phenylbenzo[d]oxazole, pzpy = 2-(1H-pyrazol-3-yl)pyridine, pzpyz = 2-(1H-pyrazol-3-yl)pyrazine). Th

PHOTOSENSITIZERS AND USE THEREOF FOR GENERATING HYDROGEN FROM WATER

The invention relates to novel complexes and to the use thereof as photosensitizers for generating hydrogen from water.

Metal-templated enantioselective enamine/H-bonding dual activation catalysis

An octahedral bis-cyclometalated iridium(III) complex catalyzes the enantioselective α-amination of aldehydes with catalyst loadings down to 0.1 mol%. In this metal-templated design, the metal serves as a structural center and provides the exclusive source of chirality, whereas the catalysis is mediated through the organic ligand sphere. This journal is the Partner Organisations 2014.

Asymmetric catalysis with an inert chiral-at-metal iridium complex

The development of a chiral-at-metal iridium(III) complex for the highly efficient catalytic asymmetric transfer hydrogenation of β,β′- disubstituted nitroalkenes is reported. Catalysis by this inert, rigid metal complex does not involve any direct metal coordination but operates exclusively through weak interactions with functional groups properly arranged in the ligand sphere of the iridium complex. Although the iridium complex relies only on the formation of three hydrogen bonds, it exceeds the performance of most organocatalysts with respect to enantiomeric excess (up to 99% ee) and catalyst loading (down to 0.1 mol %). This work hints at an advantage of structurally complicated rigid scaffolds for non-covalent catalysis, which especially relies on conformationally constrained cooperative interactions between the catalyst and substrates.

Water oxidation with molecularly defined iridium complexes: Insights into homogeneous versus heterogeneous catalysis

Molecularly defined Ir complexes and different samples of supported IrO2 nanoparticles have been tested and compared in the catalytic water oxidation with cerium ammonium nitrate (CAN) as the oxidant. By comparing the activity of nano-scaled supported IrO2 particles to the one of organometallic complexes it is shown that the overall activity of the homogeneous Ir precursors is defined by both the formation of the homogeneous active species and its conversion to IrIV-oxo nanoparticles. In the first phase of the reaction the activity is dominated by the homogeneous active species. With increasing reaction time, the influence of nano-sized Ir-oxo particles becomes more evident. Notably, the different conversion rates of the homogeneous precursor into the active species as well as the conversion into Ir-oxo nanoparticles and the different particle sizes have a significant influence on the overall activity. In addition to the homogeneous systems, IrO2@MCM-41 has also been synthesized, which contains stabilized nanoparticles of between 1 and 3 nm in size. This latter system shows a similar activity to IrCl3·xH2O and complexes 4 and 5. Mechanistic insights were obtained by in situ X-ray absorption spectroscopy and scanning transmission electron microscopy. Ir walks a fine line: Molecularly defined Ir complexes and IrO2 nanoparticles have been applied in the water oxidation reaction with cerium ammonium nitrate (CAN) as oxidant and compared (see scheme). The conversion of the first to the latter has been investigated by means of XANES, EXAFS, and STEM. Copyright

METALLIC COMPOUND AND ORGANIC ELECTROLUMINESCENCE DEVICE COMPRISING THE SAME

The present invention relates to a light emitting binuclear transition metal compound of Chemical Formulae 1 and 2, and an organic electroluminescence device including the compound. In the Chemical Formulae 1 and 2, M is selected from Ir, Pt, Rh, Re, and Os, and m is 2, provided that the m is 1 when M is Pt.

Synthesis and characterization of cyclometalated iridium(III) complexes containing benzoxazole derivatives and different ancillary ligands

The synthesis, structures, electrochemistry, and photophysics of a series of cyclometalated iridium(III) complexes based on benzoxazole derivatives and different β-diketonate ligands are reported. These complexes have a general formula C∧N2Ir(LL′) [where C∧N is a monoanionic cyclometalating ligand; 2-phenylbenzoxazolato (pbo), 2-(4-chlorophenyl)benzoxazolato (cpbo), 2-phenyl-5-chlorobenzoxazolato (pcbo), 2-(3,5-difluorophenyl)benzoxazole (fpbo), or 2-(2-naphthyl)benzoxazolato (nbo), and LL′ is an ancillary ligand; acetylacetonate (acac), dibenzoylmethanate (dbm), or 1,1,1,5,5,5-hexafluoroacetylacetonate (hfacac)]. The complexes (pcbo)2Ir(acac) (3), (dfpbo)2Ir(acac) (4), (cpbo)2Ir(dbm) (7), (dfpbo)2Ir(dbm) (8), and (dfpbo)2Ir(hfacac) (9) have been structurally characterized by X-ray crystallography. All of the complexes show reversible oxidation between 0.45 and 1.07 V, versus Fc/Fc+, and have short luminescence lifetime (τ = 0.1-1.3 μs) at room temperature. Except complex 9, the radiative decay rate (kr) and nonradiative decay rate (knr) of the (C∧N)2Ir(LL′) complexes have been determined by using the lifetime and quantum efficiency. The kr ranges between 2.0 × 103 and 3.0 × 105 s-1 and knr spans a narrower range of values (5.0 × 105 to 7.0 × 106 s-1).