Syntheses and characterization of half-sandwich zirconium complexes with dichalcogenolate o-carborane ligands

Metallocene complex (Cp2ZrCl2)-Zr-tt (Cp-tt = eta(5)-1,3-(Bu2C5H3)-Bu-t) (1) has been prepared from the reaction of LiCptt with ZrCl4 in good yield. Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands [Li(THF)(4)][(CpZr)-Zr-tt(E2C2B10H10)(2)] (E = S, 2a; E = Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X-ray analyses. In complex 2a, the Zr(IV) ion is eta(5)-bound to one 1,3-di-tert-cyclopentadienyl ring and a-bound to four mu(2)-sulfur atoms of two dithio-carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.

Syntheses, structures, and characterizations of four new silver(I) sulfonate coordination polymers with neutral ligands

In this paper, four novel silver(I) sulfonate coordination polymers containing neutral ligands, namely, [Ag(2)Ll (biim)(2)]center dot 2H(2)O (1). AgL2(biim) (2), [Ag(HL3)(Pic)(2)]center dot H2O (3), and [Ag-3(L3)(HL3)(4,4'-bipy)(3)(H2O)(2)]center dot 4H(2)O (4), have been synthesized [L1 = 3-carboxy-4-hydroxybenzenesulfonate, L2 = p-aminobenzenesulfonate, H(2)L3 = p-hydroxybenzenesulfonic acid, biim = 1,1'-(1.4-butanediyl)-bis(imidazole), Pic = beta-picoline, 4,4'-bipy = 4,4'-bipyridine]. For compounds 1 and 2, Ag(I) cations are bridged by biim ligands to form a one-dimensional (1D) "zigzag" chain, and L1 and L2 sulfonate ligands are not coordinated to the silver cation. Compound 3 has a dimeric structure in which two silver cations are bridged by two HL3 ligands. For compound 4, L3 ligand coordinates to a silver cation as a monodentate ligand, and Ag(l) cations are bridged by 4,4'-bipy ligands to form a ID chain. Compound 1 contains water dimers, while compound 4 contains water trimers. Compounds 1-3 display room-temperature photoluminescence.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Syntheses of chromium(III) complexes with Schiff-base ligands and their catalytic behaviors for ethylene polymerization

A series of chromium(III) complexes LCrCl3 (4a-c) bearing chelating 2,2'-iminodiphenyisulfide ligands [L = (2-ArMeC=NAr)(2)S] was synthesized in good yields from the corresponding ligands and CrCl3.(THF). Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display moderate activities towards ethylene polymerization, and produce highly linear polyethylenes with broad molecular weight distribution. Polymer yields, catalyst activities and the molecular weights, as well as the molecular weight distributions of the polymers can be controlled over a wide range by the variation of the structures of the chromium(III) complexes and the polymerization parameters, such as Al/Cr molar ratio, reaction temperature and ethylene pressure.

Highly efficient iridium(III) complexes with diphenylquinoline ligands for organic light-emitting diodes: Synthesis and effect of fluorinated substitutes on electrochemistry, photophysics and electroluminescence

A series of novel cyclometalated iridium(III) complexes bearing 2,4-diphenylquinoline ligands with fluorinated substituent were prepared and characterized by elemental analysis, NMR and mass spectroscopy. The cyclic voltammetry, absorption, emission and electroluminescent properties of these complexes were systematically investigated. Electrochemical studies showed that the oxidation of the fluorinated complexes occurred at more positive potentials (in the range 0.57-0.69 V) than the unfluorinated complex 1 (0.42 V). In view of the energy level, the lowering of the LUMO by fluorination is significantly less than that of the HOMO. The weak and low energies absorption bands in the range of 300-600 nm are well resolved, likely associated with MLCT and (3)pi-pi* transitions. These complexes show strong orange red emission both in the solution and solid state. The emission maxima of the fluorinated complexes showed blue shift by 9, 24 and 15 nm for 2, 3 and 4, respectively, with respect to the unfluorinated analogous 1. Multilayered organic light-emitting diodes (OLEDs) were fabricated by using the complexes as dopant materials. Significantly higher performance and lower turn-on voltage were achieved using the fluorinated complexes as the emitter than that using the unfluorinated counterpart 1 under the same doping level.

Titanium complexes with novel triaryl-substituted phosphinimide ligands: Synthesis, structure and ethylene polymerization behavior

A series of titanium phosphinimide complexes [Ph2P(2-RO-C6H4)(2)TiCl2 (7, R = CH3; 8, R = CHMe2) and (PhP(2-Me2CHOC6H4)][THF]TiCl3 (9) have been prepared by reaction of TiCl4 with the corresponding phosphinimines under dehalosilylation. The structure of complex 9 has been determined by X-ray crystallography, and a solvent molecule THF was found to be coordinated with the central metal and the Ti-O bond was consistent with the normal Ti-O (donor) bond length. The complexes 7 and 8 displayed inactive to ethylene polymerization, and the complex 9 displayed moderate activity in the presence of modified methylaluminoxane (MMAO) or i-BU3Al/Ph3CB(C6F5)(4), and this should be partly attributed to coordination of THF with titanium and the steric effect of two iso-propoxyl. And catalytic activity up to 32.2 kg-PE/(mol-Ti h bar) was observed.

Synthesis, structure and ethylene polymerization of group 4 complexes with phosphinoamide ligands

Group 4 complexes containing diphosphinoamide ligands [Ph2PNR](2)MCl2 (3: R = Bu-t, M = Ti; 4: R = Bu-t, M = Zr; 5: R = Ph, M = Ti; 6: R = Ph, M = Zr) were prepared by the reaction Of MCl4 (M = Ti; Zr) with the corresponding lithium phosphinoamides in ether or THF. The structure of [(Ph2PNBu)-Bu-t](2)TiCl2 (3) was determined by X-ray crystallography. The phosphinoamides functioned as eta(2)-coordination ligands in the solid state and the Ti-N bond length suggests it is a simple single bond. In the presence of modified methylaluminoxane or i-Bu3Al/Ph3BC(C6F5)(4), catalytic activity of up to 59.5 kg PE/mol cat h bar was observed.

Titanium and zirconium complexes with aminoiminophosphorane ligands

A series of titanium and zirconium complexes based on aminoiminophosphorane ligands [Ph2P(Nt-Bu)(NR)](2)MCl2 (4, M = Ti, R = Ph; 5, M = Zr, R = Ph; 6, M = Ti, R = SiMe3; 7, M = Zr, R = SiMe3) have been synthesized by the reaction of the ligands with TiCl4 and ZrCl4. The structure of complex 4 has been determined by X-ray crystallography. The observed very weak interaction between Ti and P suggests partial pi-electron delocalization through both Ti and P. The complexes 4-7 are inactive for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) or i-Bu3Al-Ph3CB(C6F5)(4) under atmospheric pressure, and is probably the result of low monomer ethylene concentration and steric congestion around the central metal.

Highly efficient phosphorescent bis-cyclometalated iridium complexes based on quinoline ligands

The synthesis and electrochemical and photophysical study of a series of bis-cyclometalated iridium(III) complexes based on quinoline ligands have been carried out. These complexes are found to emit red-orange to deep red phosphorescence with high quantum yield and short lifetime. The red organic light-emitting diodes (OLEDs) with the external quantum efficiency up to 11.3% were demonstrated. Slow decay of efficiency with increasing current density was observed. These indicate that quinoline-based iridium complexes are promising candidates for efficient red emitters.

Synthesis, crystal structure, spectroscopy and electroluminescence of zinc(II) complexes containing bidentate 2-(2-pyridyl)quinoline derivative ligands

Three bidentate ligands, 4-phenyl-2-(2-pyridyl)-quinoline (ppq), 6-(carbazol-9-yl)-4-phenyl-2-(2-pyridyl)-quinoline (cpq) and 6-diphenylamino-4-phenyl-2-(2-pyridyl)-quinoline (dpq) and their zinc(II) complexes, have been designed and synthesized. The crystal structure of [Zn(ppq)(2)Cl]PF6 shows that the central zinc atom is coordinated with one chloride and four nitrogen atoms from two ligands. The introduction of an electron-donating substituent such as carbazole or an aromatic amine group at the 6-position of the quinoline moiety can generate colored tunable Zn complexes, and the photoluminescence (PL) wavelength was modulated from 418 nm for [Zn(ppq)(2)Cl]PF6 to 591 nm for [Zn(cpq)(2)Cl]PF6 and 638 nm for [Zn(dpq)(2)Cl]PF6 in CH2Cl2 solution. The electroluminescence spectrum of [Zn(dpq)(2)Cl]PF6 exhibits pure red light emission with the Commission Internationale de L'Eclairage (CIE) coordinates (0.63, 0.36) and a maximum at 648 nm.

Poly[di-mu(3)-chloro-mu(2)-trans-1,2-di-4-pyridylethylene-dicopper(I)]: a two-dimensional organic-inorganic hybrid constructed from linear CuCl clusters and bridging ligands

The structure of the title compound, [Cu2Cl2(C12H10N2)](n), contains infinite CuCl staircase-like chains, which lie about inversion centres. The trans-1,2-di-4-pyrid-ylethyl-ene mol-ecules also lie about inversion centres and connect the CuCl chains through Cu-N coordination bonds into a two-dimensional organic-inorganic hybrid network. The planar sheets are stacked along the c axis and associated through weak C-H center dot center dot center dot Cl inter-actions. The results show a reliable structural motif with controllable separation of the CuCl chains by variation of the length of the ligand.

Synthesis and characterization of novel orange-emitting iridium(III) complexes with diphenylquinoline ligands containing fluorinated substituent

Three new cyclometalated iridium(III) complexes based on ligands of diphenylquinoline with fluorinated substituents were prepared, and characterized by elemental analysis (EA), H-1 NMR, and mass spectroscopy (MS). The photophysical and electrophosphorescent properties of the complexes were briefly discussed.

New neutral nickel(II) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior

New neutral nickel(II) complexes bearing nonsymmetric bidentate pyrrole-imine chelate ligands (4a-d), [2-(ArNCH)C4H3N]Ni(PPh3)Ph [Ar=2,6-diisopropylphenyl (a), 2-methyl-6-isopropylphenyl (b), 2,6-diethylphenyl (c), 2-tert-butylphenyl (d)], have been prepared in good yields from the sodium salts of the corresponding ligands and trans-Ni(PPh3)(2)(Ph)Cl, and the structure of complex 4a has been confirmed by X-ray crystallographic analysis. These neutral Ni(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce great mass polymers. Catalyst activity of up to 4.2 x 10(7) g (mol Ni h)(-1) and the viscosity-average molecular weight of polymer of up to 9.2 x 10(5) g mol(-1) were observed. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of reaction parameters such as Al-Ni ratio, norbornene-catalyst ratio, monomer concentration, polymerization reaction temperature and time.

Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.