Titanium complexes bearing aromatic-substituted β-enaminoketonato ligands: Syntheses, structure and olefin polymerization behavior

A series of titanium complexes [(Ar)NC(CF₃)CHC(R)O]₂TiCl₂ (4b: Ar = -C₆H₄OMe(p), R = Ph; 4c: Ar = -C₆H₄Me(p), R = Ph; 4d: Ar = -C₆H₄Me(o), R = Ph; 4e: Ar = α-Naphthyl, R = Ph; 4f: Ar = -C₆H₅, R = t-Bu; 4g: Ar = -C₆H₄OMe(p); R = t-Bu; 4h: Ar = -C₆H₄Me(p); R = t-Bu; 4i: Ar = -C₆H₄Me(o); R = t-Bu) has been synthesized and characterized. X-ray crystal structures reveal that complexes 4b, 4c and 4h adopt distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4b-c and 4f-i are active catalysts for ethylene polymerization and ethylene/norbornene copolymerization, and produce high molecular weight polyethylenes and ethylene/norbornene alternating copolymers. In addition, the complex 4c/MMAO catalyst system exhibits the characteristics of a quasi-living copolymerization of ethylene and norbornene with narrow molecular weight distribution.     

Palladium catalyzed Suzuki cross-coupling reactions using N,O-bidentate ligands

Palladium-catalyzed Suzuki cross-coupling reactions employing Schiff-bases as ligands toward a series of substituted arylbromides and boronic acids were pursued. In the presence of a N,O-bidentate ligand, 2-[1-(2,4,6-trimethyl-phenylimino)-ethyl]-phenol 5, the catalytic reactions could be carried out efficiently at room temperature with a wide array of arylbromides, even with electronically deactivated arenes. A deprotonated 5, 5′, chelated palladium acetate complex, [5′Pd(II)(OAc)(solv)] 8, was proposed as a precursor of a genuine catalytically active species.     

Iron‐catalyzed living radical polymerization of acrylates: Iodide‐based initiating systems and block and random copolymerizations

A half‐metallocene iron iodide complex [Fe(Cp)I(CO)₂] induced living radical polymerization of methyl acrylate (MA) in conjunction with an iodide initiator [(CH₃)₂C(CO₂Et)I, 1 ] and Al(Oi‐Pr)₃ to give polymers of controlled molecular weights and narrow molecular weight distributions (MWDs) (M_w/M_n < 1.2). With the use of chloride and bromide initiators, the MWDs were broader, whereas the molecular weights were similarly controlled. Other acrylates such as n‐butyl acrylate (nBA) and tert‐butyl acrylate (tBA) can be polymerized with 1 /Fe(Cp)I(CO)₂ in the presence of Ti(Oi‐Pr)₄ and Al(Oi‐Pr)₃, respectively, to give living polymers. The 1 /Fe(Cp)I(CO)₂ initiating system is applicable for the synthesis of block and random copolymers of acrylates (MA, nBA, and tBA) and styrene of controlled molecular weights and narrow MWDs (M_w/M_n = 1.2–1.3). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2033–2043, 2002     

Electronic structure and molecular orbital study of the first excited state of the high‐efficiency blue OLED material bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex from ab initio and TD‐B3LYP

Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq₂OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq₂OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq₂OH have been analyzed systematically to study the electronic transition mechanism in AlMq₂OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq₂OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S₁) of AlMq₂OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S₀ → S₁) of AlMq₂OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq₂OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al³⁺. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq₂OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

乙酰丙酮钇催化环氧氯丙烷的均聚合与共聚合

用过渡金属络合催化剂聚合环氧氯丙烷能获高分子量的聚合物。稀土络合催化剂对环氧乙烷,环氧丙烷及环硫丙烷的开环聚合具有明显效果。本文选用Y(acac)_3-H_2O-Al(i-Bu)_3催化剂,考察环氧氯丙烷的均聚合及其与环氧乙烷,环氧丙烷的共聚合,并用核     

Trans-cis Photoisomerization of 1-Methyl-4-(4′-hydroxystyryl)pyridinium in inclusion complexes ofβ-cyclodextrin and its derivatives

The effects of -cyclodextrin (-CyD), heptakis(2,6-di-O-methyl)--cyclodextrin (DMCyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMCyD) ontrans-cis photoisomerization of 1-ethyl-4-(4-hydroxystyryl)pyridinium (POH) have been studied in aqueous solutions. The ratio of [cis]/[trans] for POH in the photostationary state at pH 8.54 was remarkably reduced by the presence of CyD or DMCyD. The reduction of the [cis]/[trans] ratio in the photostationary state was explained in terms of the shift of the equilibrium of POH ₊ ^trans PO _trans + H^– toward PO _trans formation. The binding constants of CyD and DMCyD for PO _trans were 2.00- and 1.36-fold larger than those for POH ₊ ^trans , respectively. The binding constants of TMCyD for both species are much smaller than those of CyD and DMCyD. This result indicates that PO _trans , which has a betain structure, forms stable complexes with CyD and DMCyD with its hydrophobic parts inside and the charged parts outside the CyD cavities.     

Semiempirical PM5 molecular orbital study on chlorophylls and bacteriochlorophylls: comparison of semiempirical, ab initio, and density functional results

The semiempirical PM5 method has been used to calculate fully optimized structures of magnesium-bacteriochlorin, magnesium-chlorin, magnesium-porphin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), and d, and bacteriochlorophylls a, b, c, d, e, f, g, and h with all homologous structures. Hartree-Fock/6-31G* ab initio and density functional B3LYP/6-31G* methods were used to optimize structures of methyl chlorophyllide a, chlorophyll c(1), and methyl bacteriochlorophyllides a and c for comparison. Spectroscopic transition energies of the chromophores and their 1:1 or 1:2 solvent complexes were calculated with the Zindo/S CIS method. The self-consistent reaction field model was used to estimate solvent shifts. The PM5 calculations predict planar structure of the porphyrin ring and central position of the four coordinated magnesium atoms in all pigments studied, in accord with the experimental, ab initio, and density functional results, a significant improvement as compared to the older semiempirical PM3 approach. Only small differences in PM5 and B3LYP/6-31G* or Hartree-Fock/6-31G* minimum energy geometries of the reference molecules were observed. Calculations show that in 1:1 solvent complexes, where the magnesium atom is five coordinated, the magnesium atom is shifted out of the plane of the porphyrin ring towards the solvent molecule, while the hexa coordinated 1:2 complexes are again planar. The PM5 method gives atomic charges that are comparable with those obtained from the Hartree-Fock/6-31G* and B3LYP/6-31G* calculations. The single point ZINDO/S CIS calculations with PM5 minimum energy structure gave excellent correlations between calculated and experimental transition energies of the chlorophylls and bacteriochlorophylls studied. Such correlations may be used for prediction of transition energies of the chromophores in protein binding sites. Calculations also predict existence of dark electronic states below the main Soret absorption band in all chromophores studied. The results suggest that the semiempirical PM5 method is a fairly reliable and computationally efficient method in predicting molecular parameters of porphyrin-like molecules.     

Purines, pyrimidines, and related fused systems. 20. Heterocyclizations of 6-alkynyl-1,3-dimethyllumazines. Synthesis of pyrrole and thiophene analogs of some natural pteridines

Sonogashira cross-coupling of 6-chloro-1,3-dimethyllumazine with terminal alkynes gave 6-alkynyl derivatives in good yields. Oxidative amination of the latter with primary alkylamines was accompanied by the pyrrole-ring closure to form 1-R"-2-R-6,8-dimethylpyrrolo[3,2-g]pteridine-5,7(6H,8H)-diones. The addition of bromine to 6-alkynyllumazines afforded the corresponding dibromoalkenes whose treatment with sodium trithiocarbonate gave rise to 2-R-6,8-dimethylthieno[3,2-g]pteridine-5,7(6H,8H)-diones. The latter compounds are close analogs of the metabolite of molybdenum cofactor (molybdopterine).     

A quantum chemical study on the mechanism of S-coordinated tetrazole-thiolato formation by the reaction of organic isothiocyanates with metal azido complexes of Pt(II), Pd(II), and Sn

The mechanism of the reaction of isothiocyanates with metal-azido complexes of Pt(II), Pd(II), and Sn as well as hydrazoic acid is studied using the density functional theory method. The relative stability between two possible product isomers (S-coordinated tetrazole-thiolato and N-coordinated tetrazolato complexes) does not directly relate to the experimentally synthesized product. The overall reaction proceeds via three steps. The first step is the approach of the S-atom of the organic isothiocyanate to the central metal atom followed by the nucleophilic attack of the coordinated N-atom of the azido group to the C-atom of the isothiocyanate. The activation barrier of this step is 22-24 kcal mol⁻¹, and the resulting intermediate has the imidoyl azide form. In the second reaction step, electrophilic attack of the terminal N-atom of the azido group to the N-atom of the isothiocyanate transforms the intermediate to the S-coordinated tetrazole-thiolato product with a barrier of about 11 kcal mol⁻¹. The N-coordinated tetrazole could be made from the S-coordinated tetrazole-thiolato complex only after the third step, in which the metal coordination migrates from the S- to the N-atom.     

SYNTHESIS AND CHARACTERIZATIONS OF NEAR INFRARED ABSORBING POLYMERS

A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]~(n ) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M~(-1)cm~(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm).