2633-66-1Relevant articles and documents
Backbone Boron-Functionalized Imidazoles/Imidazolium Salts: Synthesis, Structure, Metalation Studies, and Fluoride Sensing Properties
Anantharaman, Ganapathi,Avinash, Iruthayaraj,Parveen, Sabeeha
, (2020)
Incorporation of a Lewis acidic BMes2 (Mes = mesityl) moiety at the backbone of the imidazole ring was achieved by metal-halogen exchange procedure. Among them, two isomeric boron-phosphine functionalized imidazoles (3 and 6), monoboron-functionalized imidazoles (4 and 5), and its corresponding imidazolium salts were synthesized and thoroughly characterized. The solid-state structure of 3 reveals a dimeric B-N adduct that possesses six-membered [C-B-N]2 ring, and 5 crystallizes as tetrameric B-N adduct that forms an interesting 16-membered macrocycle, whereas 4 and 6 were obtained as monomeric BMes2-substituted imidazoles. 6 behaves as a P^N-type ligand upon the coordination with CuI to afford luminescent L2Cu4I4-type metal complexes (10 and 11) whose photophysical properties were also studied. The presence (in 10) and the absence (in 11) of BMes2 made a remarkable impact on fluorescence emission causing shift from the green (10) to orange (11) region. The fluoride sensing properties of BMes2-containing imidazoles (4 to 9) were studied using UV-vis and fluorescence spectroscopy.
Cyclopalladation of telluro ether ligands: Synthesis, reactivity and structural characterization
Kolay, Siddhartha,Kumar, Mukesh,Wadawale, Amey,Das, Dasarathi,Jain, Vimal K.
supporting information, p. 16056 - 16065 (2015/01/09)
Treatment of [PdCl2(PhCN)2] with diaryl telluride in 1:2 molar ratio gave mononuclear palladium complexes, trans-[PdCl2(TeR2)2] (1) (R = Mes (1a) (Mes = 2,4,6-trimethylphenyl), Ph (1b), o-tol (1c) (o-tol = ortho-tolyl)). Reaction of [PdCl2(TeMes2)2] with one equivalent of [PdCl2(PhCN)2] or Na2PdCl4 with TeRR′ afforded chloro-bridged binuclear complexes, [Pd2(μ-Cl)2Cl2(TeRR′)2] (2) (R/R′ = Mes/Mes (2a); Mes/Ph (2b); Ph/Ph (2c)). A toluene-methanol solution of trans-[PdCl2(TeMes2)2] on refluxing for 30 minutes yielded a binuclear cyclopalladated complex, [Pd2(μ-Cl)2{CH2C6H2(4,6-Me2)TeMes)}2] (3). When the refluxing was prolonged, a mononuclear complex cis-[PdCl2{MesTeCH2C6H2(4,6-Me2)TeMes}] (4) was isolated. Treatment of palladium acetate with TeMes2 afforded an acetato-bridged analogue of 3, [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeMes}2] (5a) together with a very minor component, a tetranuclear complex, [Pd(μ-OAc)(μ-TeMes)]4 (6). This reaction with unsymmetrical tellurides, MesTeR, also gave cyclopalladated complexes [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeR}2] (R = o-tol (5b) and Ph (5c)) in which 2-methyl of the mesityl group of the telluride was exclusively metallated. The complex trans-[PdCl2(TeMes2)2] on refluxing in xylene gave palladium telluride, Pd7Te3. These complexes were characterized by elemental analyses, IR and NMR (1H, 13C and 125Te) spectroscopy. The molecular structures of trans-[PdCl2(TeMes2)2] (1a), [Pd2(μ-Cl)2Cl2(TeMes2)2]·2acetone (2a·2acetone), cis-[PdCl2{MesTeCH2C6H2(4,6-Me2)TeMes}] (4), [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeMes)}2]·toluene (5a·toluene), [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)Tetol-o}2] (5b) and [Pd(μ-OAc)(μ-TeMes)]4 (6) were established by single crystal X-ray diffraction analyses. The mononuclear complex 1a was isolated in two polymorphic forms each with the trans configuration. This journal is
Cyclometalated iridium complexes of bis(aryl) phosphine ligands: Catalytic C-H/C-D exchanges and C-C coupling reactions
Campos, Jesus,Espada, Maria F.,Lopez-Serrano, Joaquin,Carmona, Ernesto
supporting information, p. 6694 - 6704 (2013/07/19)
This work details the synthesis and structural identification of a series of complexes of the (η5-C5Me5)Ir(III) unit coordinated to cyclometalated bis(aryl)phosphine ligands, PR′(Ar) 2, for R′ = Me and Ar = 2,4,6-Me3C6H 2, 1b; 2,6-Me2-4-OMe-C6H2, 1c; 2,6-Me2-4-F-C6H2, 1d; R′ = Et, Ar = 2,6-Me2C6H3, 1e. Both chloride-and hydride-containing compounds, 2b-2e and 3b-3e, respectively, are described. Reactions of chlorides 2 with NaBArF (BArF = B(3,5-C 6H3(CF3)2)4) in the presence of CO form cationic carbonyl complexes, 4+, with ν(CO) values in the narrow interval 2030-2040 cm-1, indicating similar π-basicity of the Ir(III) center of these complexes. In the absence of CO, NaBArF forces κ4-P,C,C′,C″ coordination of the metalated arm (studied for the selected complexes 5b, 5d, and 5e), a binding mode so far encountered only when the phosphine contains two benzylic groups. A base-catalyzed intramolecular, dehydrogenative, C-C coupling reaction converts the κ4 species 5d and 5e into the corresponding hydrido phosphepine complexes 6d and 6e. Using CD3OD as the source of deuterium, the chlorides 2 undergo deuteration of their 11 benzylic positions whereas hydrides 3 experience only D incorporation into the Ir-H and Ir-CH 2 sites. Mechanistic schemes that explain this diversity have come to light thanks to experimental and theoretical DFT studies that are also reported.