- Catalytic Addition of Alcohols into Carbodiimides Promoted by Organoactinide Complexes
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The insertion of alcohols into carbodiimides mediated by benzimidazolin-2-iminato actinide complexes [(BimR1/R2N)AnN3] [N = N(SiMe3)2] is presented herein. Analysis of single-crystal data revealed that steric hindrance, rather than electronic properties, plays an important role in determining the accessibility for this insertion process. All actinide complexes showed excellent activities under very mild conditions. Stoichiometric reactions in combination with kinetic and thermodynamic studies allow us to propose a plausible active species and a mechanism for the catalytic cycle.
- Liu, Heng,Khononov, Maxim,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
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Read Online
- “Give me five” - an amino imidazoline-2-imine ligand stabilises the first neutral five-membered cyclic triel(i) carbenoides
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We present the first cyclic five-membered triel(i) carbenoides E(AmIm) for E = Ga, In, Tl; AmIm = amido imidazoline-2-imine, which fill the current gap between four- and six-membered triel(i) carbenoides supported by HGiso and HNacNac. Ga(AmIm) can act as a strong σ-donor ligand in transition metal complexes, while the intermediacy of the Al(i) carbenoide Al(AmIm) is rationalised based on the isolation of an Al(iii) insertion product.
- Denker, Lars,Trzaskowski, Bartosz,Frank, René
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Read Online
- Molecular Scissors for Tailor-Made Modification of Siloxane Scaffolds
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The controlled design of functional oligosiloxanes is an important topic in current research. A consecutive Si?O?Si bond cleavage/formation using siloxanes that are substituted with 1,2-diaminobenzene derivatives acting as molecular scissors is presented.
- Bauer, Jonathan O.,Falk, Alexander,G?tz, Tobias
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supporting information
(2021/12/09)
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- Addition of E-H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes
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The synthesis and characterization of benzimidazolin-2-iminato actinide(IV) complexes [(BimR1/R2N)An(N{SiMe3}2)3] (An = U, Th) (1-6) is reported. All complexes were obtained in high yields, and their solid state structures were established through single-crystal X-ray diffraction analysis. Using 1-6 as precatalysts, the addition of mono- and bifunctional E-H (E = N, P, C, O, S) substrates to various heterocumulenes, including carbodiimides, isocyanates, and isothiocyanates, was investigated, affording the respective addition products in high yields under very mild reaction conditions. Various amines were applicable to this reaction, indicating a large scope capability of amine nucleophiles for the insertion process.
- Liu, Heng,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
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supporting information
p. 3896 - 3903
(2017/10/30)
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- Highly phosphorescent cyclometalated platinum(II) complexes based on 2-phenylbenzimidazole-containing ligands
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A series of tetradentate cyclometalated platinum(ii) complexes (Pt 1, Pt 2, and Pt 3) based on 2-phenylbenzimidazole-containing ligands have been prepared. Their photophysical properties were investigated by absorption and emission spectroscopy as well as density functional theory calculations. Due to the robustness of their coordination frameworks, these Pt(ii) complexes exhibited excellent thermal stabilities with decomposition temperatures above 400 °C. The 2-phenylbenzimidazole motif was functionalized with a twisted aryl group, which discouraged intimate intermolecular interactions, thus leading to constant CIE coordinates at different doping ratios. The effect of replacing a coordinating pyridine group by thiazole and oxazole on photophysical properties, electrochemical behaviors, and electroluminescence performance was studied. Single crystal X-ray diffraction analyses of Pt 1 revealed a weak intra-molecular interaction, particularly a negligible Pt?Pt interaction, in the solid state, which was consistent with its electroluminescence properties at a high doping level. Organic light emitting diodes (OLEDs) based on these Pt(ii) complexes were fabricated with a typical multiple layered device configuration. Among the three Pt(ii) complexes, the pyridine-based Pt 1 compound showed the highest electroluminescence performance with maximum CE, PE, and EQE of 78.5 cd A-1, 66.4 lm W-1, and 22.3%, respectively.
- Li, Jing,Liang, Feng,Zhao, Yue,Liu, Xiang-Yang,Fan, Jian,Liao, Liang-Sheng
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supporting information
p. 6202 - 6209
(2017/07/10)
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- Phosphorescent material
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Heteroleptic compounds containing phenylpyridine and phenylbenzimidazole are provided. The compounds may be used in organic light emitting devices, particularly as emissive dopants in the emissive layer of such devices.
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Paragraph 0108; 0109
(2017/02/24)
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- ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
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A compound having a Pt tetradentate structure selected from the group consisting of is provided. In the structures of Formula 1 and Formula 2, rings C and D each independently represent 5- or 6-membered carbocyclic or heterocyclic ring; L1, Ls
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Paragraph 0124-0125
(2016/09/12)
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- Organic Electroluminescent Materials and Devices
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A new class of blue emissive complexes are described. The compounds comprise pyridyl benzimidazole ligands with twisted aryl groups for improved color.
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Paragraph 0144-0145
(2016/10/11)
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- Nitrene Insertion into C-C and C-H Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron
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The impact of redox non-innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{-CH£N(1,2-C6H4)NH(2,6-iPr2C6H3)}2]n (n=0 to -4), (dadi)n, chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d4 Cr configuration antiferromagnetically coupled to (dadi)2-, and [1Fe] to be S=2. Treatment with RN3 provides products where RN is formally inserted into the C-C bond of the diimine or into a C-H bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens.
- Heins, Spencer P.,Morris, Wesley D.,Wolczanski, Peter T.,Lobkovsky, Emil B.,Cundari, Thomas R.
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supporting information
p. 14407 - 14411
(2016/01/25)
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- A comparison between oxazoline-imidazolinylidene, -imidazolylidine, -benzimidazolylidene hydrogenation catalysts
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Imidazolinylidene, imidazolylidine, benzimidazolylidene complexes 1a-c were prepared and tested in asymmetric hydrogenations of a series of largely unfunctionalized alkenes. Similarities and differences in the catalytic performance of these complexes were rationalized in terms of the predicted mechanisms of these reactions, and their relative tendencies to generate protons under the hydrogenation conditions.
- Khumsubdee, Sakunchai,Fan, Yubo,Burgess, Kevin
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p. 9969 - 9974
(2013/10/22)
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- NOVEL HETEROLEPTIC IRIDIUM COMPLEXE
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Novel heteroleptic iridium complexes are disclosed. The complexes contain a phenyl pyridine ligand and another ligand containing a dibenzofuran, dibenzothiophene, dibenzoselenophene, or carbazole linked to an imidazole or benzimidazole fragment. These complexes are useful materials when incorporated into OLED devices.
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Page/Page column
(2013/07/25)
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- PHOSPHORESCENT HETEROLEPTIC PHENYLBENZIMIDAZOLE DOPANTS AND NEW SYNTHETIC METHODOLOGY
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Novel heteroleptic iridium complexes are provided. These iridium complexes are useful compounds in OLED devices. The ligands for these novel complexes may be obtained using a new synthetic methodology that utilizes manganese dioxide.
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Page/Page column 66
(2012/12/13)
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