Synthesis and luminescence of poly(phenylacetylene)s with pendant iridium complexes and carbazole groups
Poly(phenylacetylene)s containing pendant phosphorescent iridium complexes have been synthesized and their electrochemical, photo- and electroluminescent properties studied. The polymers have been synthesized by rhodium-catalyzed copolymerization of 9-(4-ethynylphenyl)carbazole (CzPA) and phenylacetylenes (C∧N)2Ir(κ2-O,O′-MeC(O)CHC(O)C6H4CCH-4) (C∧N = κ2-N,C1-2-(pyridin-2-yl)phenyl (IrppyPA) or κ2-N,C1-2-(isoquinolin-1-yl)phenyl (IrpiqPA)). In addition, organic poly(phenylacetylene)s with pendant carbazole groups have been synthesized by rhodium-catalyzed copolymerization of CzPA and 1-ethynyl-4-pentylbenzene. Complex (C∧N)2Ir(κ2-O,O′-MeC(O)CHC(O)Ph) (IrpiqPh; C∧N = 2-(isoquinolin-1-yl)phen…
Erosion, screening, and migration of tungsten in the JET divertor
The erosion of tungsten (W), induced by the bombardment of plasma and impurity particles, determines the lifetime of plasma-facing components as well as impacting on plasma performance by the influx of W into the confined region. The screening of W by the divertor and the transport of W in the plasma determines largely the W content in the plasma core, but the W source strength itself has a vital impact on this process. The JET tokamak experiment provides access to a large set of W erosion-determining parameters and permits a detailed description of the W source in the divertor closest to the ITER one: (i) effective sputtering yields and fluxes as function of impact energy of intrinsic (Be,…
Synthesis and solution behavior of some bis[2-{(dimethylamino)methyl}phenyl]gold(III) complexes
Abstract [Au(2-C6H4CH2NMe2)Cl2] reacts with [Hg(2-C6H4CH2NMe2)2] (2/1) or with [Hg(2-C6H4CH2- NMe2)Cl] (1/1) both in the presence of an excess of [Me4N]Cl to give [Au(2-C6H4CH2NMe2)2Cl] (1) which reacts with KCN or AgClO4 to give [Au(2- C6H4CH2-NMe2)2CN] (2) or [Au(2-C6H4CH2- NME2)2]ClO4 (3), respectively. The solution behavior of these complexes is studied by NMR spectroscopy.
Mercurated and Palladated Iminophosphoranes. Synthesis and Reactivity
Reaction of the iminophosphorane Ph3PNC6H4Me-4 (1a) with Hg(OAc)2 and LiCl gives the mercurated iminophosphorane [Hg{C6H3(NPPh3)-2-Me-5}Cl] (2). The latter reacts with NaBr to give [Hg{C6H3(NPPh3)-2-Me-5}Br] (3). 2 reacts with MeC6H4NCO-4 or CX2 (X = O, S) to give [Hg{C6H3(NCNC6H4Me-4‘)-2-Me-5}Cl] (4) or [Hg{C6H3{NCNC6H3(HgCl)-1‘-Me-5‘}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph3PNC6H4R-4 (1b) react with Pd(OAc)2 to give the complexes [Pd{κ2-C,N-C6H4(PPh2NC6H4R-4‘)-2}(μ-OAc)]2 (R = Me (6a), MeO (6b)), in which the palladation takes place at one of the phenyl substituents of the PPh3 group. Complex 6b reacts with NaBr or tBuNC to give [Pd{κ2-C,N-C6H4(PPh2NC6H4OMe-4‘)-2}(μ-Br)]2 (7) o…
Mono- and di-nuclear complexes of ortho-palladated and -platinated 4,4′-dimethylazobenzene with bis(diphenylphosphino)methane. More data on transphobia
Abstract Complexes [Pd(κ2-R)(μ-Cl)]2 [κ2-R=κ2-C,N′-C6H3(NNC6H4Me-4′)-2-Me-5 (1)] and [Pd(κ1-R)Cl(κ1-dppm)(κ2-dppm)]TfO [dppm=bis(diphenylphosphino)methane (2)] have been used to prepare new palladium derivatives containing dppm. Thus, complex 1 reacts with one equivalent of dppm to afford [{Pd(κ2-R)Cl}2(μ-dppm)] (3) and with AgClO4 and dppm (1:2:2 molar ratios) to give [Pd(κ2-R)(κ2-dppm)]ClO4 (4·ClO4). The triflate salt of this complex (4·TfO) reacts with PPh3 to yield [Pd(κ1-R)(PPh3)(κ2-dppm)]TfO (5). Dinuclear complexes were obtained by reacting 2, (i) with [AuCl(PPh3)] or [AuCl(tht)] (tht=tetrahydrothiophene) (1:1, −60 °C) and (ii) with 1 (2:1) to give, respectively, [Pd(κ1-R)Cl(μ-dppm…
New Carbenegold(I) Complexes Synthesized by the “Acac Method”
The reaction of [AuCl{C(NEt2)NHtBu}] with Tl(acac)] (1:1) gives [Au(C-acac){C(NEt2)NHtBu}] (1). Complex 1 reacts with 2-pyridinethiol (HSpy-2), C6H4(C⋮CH)2−1,3 (2:1), [Ph3PCH2CO2Me]ClO4, [Me3S(O)]ClO4, or [Me3NH]ClO4 to give, respectively, [Au(Spy-2){C(NEt2)NHtBu}] (2), [{AuC(NEt2)NHtBu}2(μ−C⋮CC6H4C⋮C-3)] (3), [Au{C(NEt2)NHtBu}{CH(PPh3)CO2Me}]ClO4 (4), [Au{C(NEt2)NHtBu}{CH2S(O)Me2}]ClO4 (5), or [Au{C(NEt2)NHtBu}(NMe3)]ClO4 (6). The crystal structures of 1, 3, and 5 have been determined.
Synthesis and Reactivity toward Isonitriles of (2-Aminoaryl)palladium(II) Complexes
Mixtures of “Pd(dba)2” (dba = dibenzylideneacetone) and 2,2‘-bipyridine (bpy; 1:2) or N,N,N‘,N‘-tetramethylethylenediamine (tmeda; 1:1) react with 2-bromo-4-nitroaniline to give [Pd{C6H3NH2-2-NO2-5}Br(N−N)] (N−N = bpy (1b), tmeda (1b‘)). Reactions of 2-iodoaniline with mixtures of “Pd(dba)2” and isonitriles RNC (R = C6H3Me2-2,6 (Xy), 2:1:2 molar ratios; R = tBu, 2.9:1:2 molar ratios) result in the formation of the complexes [Pd{κ2C,N-C(NXy)C6H4NH2-2}I(CNXy)] (2a) and trans-[Pd{C(NtBu)C6H4NH2-2}I(CNtBu)2] (3a*). The reactions of [Pd{C6H4NH2-2}I(bpy)] and 1b‘ with RNC give the complexes trans-[Pd{C(NR)C6H3NH2-2-Y-5}}X(CNR)2] (Y = H, X = I, R = Xy (3a), tBu (3a*); Y = NO2, X = Br, R = Xy (3b),…
Overview of the JET results in support to ITER
The 2014–2016 JET results are reviewed in the light of their significance for optimising the ITER research plan for the active and non-active operation. More than 60 h of plasma operation with ITER first wall materials successfully took place since its installation in 2011. New multi-machine scaling of the type I-ELM divertor energy flux density to ITER is supported by first principle modelling. ITER relevant disruption experiments and first principle modelling are reported with a set of three disruption mitigation valves mimicking the ITER setup. Insights of the L–H power threshold in Deuterium and Hydrogen are given, stressing the importance of the magnetic configurations and the recent m…
Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes
The arylmercurial [Hg{C6H3(CHO)2-2,5}Cl] (1) reacts with CH(OMe)3 or HS(CH2)2SH to give [Hg{C6H3{CH(OMe)2}2-2,5}Cl] (2) or [Hg(Ara)Cl] [Ara = C6H3{CH(SCH2CH2S)}2-2,5 (3a)], respectively. The mercur...
Structure, tritium depth profile and desorption from 'plasma-facing' beryllium materials of ITER-Like-Wall at JET
This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014–2018 under grant agreement No 633053 . The views and opinions expressed herein do not necessarily reflect those of the European Commission.
Ortho-Metalated Primary Amines. 6.1 The First Synthesis of Six-Membered Palladacycles from Primary Amines Containing Electron-Withdrawing Substituents: End of the Limiting Rules of Cope and Friedrich on Cyclopalladation of Benzyl- and Phenethylamines
When H 2 N(CH 2 ) 2 C 6 H 4 OMe-4 (RNH 2 ) and Pd(OAc) 2 are reacted in a 2:1 molar ratio, the complex [Pd(OAC) 2 (NH 2 R) 2 ] (1) is obtained. Complex 1 reacts with 1 equiv of Pd(OAc) 2 to give the dinuclear complex [Pd(OAc)(μ-OAc)(NH 2 R)] 2 (2). When complex 2 is heated in acetonitrile at 80 °C, the ortho-metalated complex [Pd{C 6 H 3 (CH 2 ) 2 NH 2 -2-OMe-5-κ 2 C,N}(μ-OAc)] 2 (3a) is obtained. Complex 3a is also prepared by refluxing RNH 2 and Pd(OAc) 2 in a 1:1 molar ratio in acetonitrile. Complex 3a reacts with NaBr or LiCl to afford the complexes [Pd{C 6 H 3 (CH 2 ) 2 NH 2 -2-OMe-5-κ 2 C,N}(μ-X)]2 (X = Cl (3b), Br (3c)). PPh 3 splits the acetate or halide bridge in complex 3a or 3b t…
Synthesis and Reactivity of 2-Aminophenylpalladium(II) Complexes: Insertion Reactions of Oxygen and Carbon Monoxide into Carbon−Palladium Bonds—New Examples of “Transphobia”
Insertion of CO into 2-aminophenylpalladium complexes leads to 2-aminobenzoylpalladium derivatives. When these compounds are forced to coordinate a carbon donor and a phosphane ligand in the trans position, a C−P coupling process or an insertion of oxygen occurs (see scheme). In this case, a dinuclear palladium complex containing a bridging anthranilato ligand is isolated.
Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C Bond of Ortho-palladated Primary and Secondary Arylalkylamines
The ortho-metalated complex [Pd2{κ2(C,N)-C6H4CH2CH2NHMe-2}2(μ-Br)2] (1) can be prepared by refluxing a 1:1 mixture of Pd(OAc)2 and N-methylphenethylamine in acetonitrile, followed by addition of an excess of NaBr. Complex 1 reacts with PPh3 to give the mononuclear derivative [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}Br(PPh3)] (2). The cationic complex [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}(py)2]ClO4 (3) can be obtained by reacting 1 with AgClO4 and pyridine. The previously reported complex [Pd2{κ2(C,N)-C6H4CH2NHCH2Ph-2}2(μ-Br)2] (A) reacts with PhC≡CCO2R (R = Me, Et) to give the monoinserted derivatives [Pd2{κ2(C,N)-C(Ph)═C(CO2R)C6H4CH2NHCH2Ph-2}2(μ-Br)2] (R = Me (4a), Et (4b)). These dimers react with neutral l…