Chlorido[2-(diphenyl­phos­phino)­aceto­phenone]gold(I)

In the crystal structure of the title compound, [AuCl(C20H17OP)], the phosphine acts as a monodentate ligand. The Au atoms are attached solely to the P and Cl atoms. The coordination is linear without any tendency to aggregate via aurophilic inter­actions

μ-Bis(diphenyl­arsino)methane-κ2 As:As′-bis­[chloridogold(I)]

The title structure, [Au2Cl2(C25H22As2)], consists of discrete mol­ecules disposed about a crystallographic twofold axis. The Au atom exhibits a nearly linear coordination by As and Cl atoms. Au⋯Au inter­actions [3.4285Å(4) Å] and a weak intermolecular C—H⋯Cl hydrogen bond are present

Tricarbonyl­chlorido{N-[2-(diphenyl­phosphino)benzyl­idene]benzyl­amine-κ2 N,P}rhenium(I) dichloro­methane solvate

In the crystal structure of the title compound, [ReCl(C26H22NP)(CO)3]·CH2Cl2, the ReI atom exhibits a distorted octa­hedral environment defined by a facial arrangement of three carbonyl groups, a Cl atom and an N-[2-(diphenyl­phosphino)benzyl­idene]benzyl­amine ligand. The compound crystallizes with one CH2Cl2 mol­ecule per asymmetric unit. The benzyl­amine ligand and the ReI centre form a non-planar six-membered chelate ring

Tetra­kis(triphenyl­arsine)copper(I) hexa­fluoridophosphate

In the crystal structure of the title compound, [Cu(C18H15As)4]PF6, the Cu atom is coordinated by four As atoms of triphenyl­arsine ligands in a tetra­hedral geometry. The complex cation is located on a crystallographic threefold axis. Both PF6 − anions are located on special positions of site symmetry . The Cu—As bond of the independent arsine ligand is shorter than the Cu—As bonds of the three symmetry-related arsine ligands

{Bis[2-(diphenyl­phosphan­yl)phen­yl] ether-κ2 P,P′}(1,1′-dibenz­yl-1H,1′H-4,4′bi-1,2,3-triazole-κ2 N3,N 3′)copper(I) hexa­fluorido­phosphate dichloro­methane hemisolvate

In the crystal structure of the title compound, [Cu(C18H16N6)(C36H28OP2)]PF6·0.5CH2Cl2 or [Cu(DPEPhos)(Bn-bta)]PF6·0.5CH2Cl2 {DPEPhos = bis­[(diphenyl­phosphan­yl)phen­yl] ether and Bn-bta = 1,1′-dibenzyl-1H,1′H-4,4′-bi-1,2,3triazol­e}, the Cu atom is coordinated by two N and two P atoms of the ligands in a strongly distorted tetra­hedral environment. There are two crystallographically independent complex cations present, which differ significantly in their geometrical parameters. The solvent molecule is disordered but satisfactory atomic positions could not be determined

Isothiourea-catalyzed enantioselective functionalisation of glycine Schiff base aryl esters via 1,6- and 1,4-additions

The St Andrews team thanks the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, grant code EP/L016419/1) (RC) for funding. The Linz team gratefully acknowledges generous financial support by the Austrian Science Funds (FWF) through project No. P31784.The enantioselective α-functionalisation of glycine Schiff base aryl esters through isothiourea catalysis is successfully demonstrated for 1,6-additions to para-quinone methides (21 examples, up to 95 : 5 dr and 96 : 4 er) and 1,4- additions to methylene substituted dicarbonyl or disulfonyl Michael acceptors (17 examples, up to 98 : 2 er). This nucleophilic organocatalysis approach gives access to a range of α-functionalised α-amino acid derivatives and further transformations of the activated aryl ester group provide a straightforward entry to advanced amino acid-based esters, amides or thioesters.Publisher PDFPeer reviewe

Green-light photocleavable meso-methyl BODIPY building blocks for macromolecular chemistry

We report the design of easily accessible, photocleavable meso-methyl BODIPY monomers suitably functionalised for incorporation into macromolecules. Firstly a BODIPY-diol as a novel AA-type bifunctional monomer is reported. Secondly, from the same common BODIPY precursor, a clickable, azide functionalised AB-type hetero-bifunctional monomer was prepared. Photochemical studies of model compounds confirmed the ability of these compounds to undergo photocleavage in green light (lambda > 500 nm). Their usefulness for photoclippable macromolecular systems is then demonstrated: firstly by incorporating the diols into polyurethane hydrogels shown to undergo photocleavage and hence dissolution under visible light irradiation and secondly, the preparation of water-soluble macromolecular photocages able to photorelease small molecules. Thus the results presented herein describe a proof-of-principle for BODIPY-based photoresponsive materials, for example, for use as degradable polymers, sacrificial materials for lithography or for the delivery of caged pharmaceuticals

Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure

[EN] A series of alkyltributylphosphonium chloride ionic liquids, prepared from tributylphosphine and the respective 1-chloroalkane, CnH2n+1Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids, where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl) phosphonium chloride is detailed.This work was funded by Cytec Canada, Inc. G.A. would like to thank Dr Douglas Harris (Cytec) for fruitful comments and advice at the beginning of this work; Prof. Chris Strauss, Dr Markus Fanselow and Dr Giulia Fiorani for microwave assistance and helpful guidance, and Prof. P.R. Raithby for the X-ray diffraction data collection. L.P.N.R. thanks Fundacao para a Ciencia e Tecnologia, Portugal, for support under grants PTDC/QUI-QUI/101794/2008 and PTDC/QUI/71331/2006.Adamova, G.; Gardas, RL.; Nieuwenhuyzen, M.; Vaca Puga, A.; Rebelo, LPN.; Robertson, AJ.; Seddon, KR. (2012). Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure. Dalton Transactions. 41(27):8316-8332. doi:10.1039/c1dt10466gS83168332412

Luminescent osmium(II) bi-1,2,3-triazol-4-yl complexes: photophysical characterisation and application in light-emitting electrochemical cells

The series of osmium(II) complexes [Os(bpy)3-n(btz)n][PF6]2 (bpy = 2,2’-bipyridyl, btz = 1,1’-dibenzyl-4,4’-bi-1,2,3-triazolyl, 1 n = 0, 2 n = 1, 3 n = 2, 4 n = 3), have been prepared and characterised. The progressive replacement of bpy by btz leads to blue-shifted UV-visible electronic absorption spectra, indicative of btz perturbation of the successively destabilised bpy-centred LUMO. For 4, a dramatic blue-shift relative to the absorption profile for 3 is observed, indicative of the much higher energy LUMO of the btz ligand over that of bpy, mirroring previously reported data on analogous ruthenium(II) complexes. Unlike the previously reported ruthenium systems, heteroleptic complexes 2 and 3 display intense emission in the far-red/near-infrared (λmax = 724 and 713 nm respectively in aerated acetonitrile at RT) as a consequence of higher lying, and hence less thermally accessible, 3MC states. This assertion is supported by ground state DFT calculations which show that the dσ* orbitals of 1 to 4 are destabilised by between 0.60 and 0.79 eV relative to their Ru(II) analogues. The homoleptic complex 4 appears to display extremely week room temperature emission, but on cooling to 77 K the complex exhibits highly intense blue emission with λmax 444 nm. As complexes 1 to 3 display room temperature luminescent emission and readily reversible Os(II)/(III) redox couples, light-emitting electrochemical cell (LEC) devices were fabricated. All LECs display electroluminescent emission in the deep-red/near-IR (λmax = 695 to 730 nm). Whilst devices based on 2 and 3 show inferior current density and luminance than LECs based on 1, the device utilising 3 shows the highest external quantum efficiency at 0.3 %