The effect of the amido substituent on polymer molecular weight in propene homopolymerisation by titanium cyclopentadienyl-amide catalysts

In the homopolymerisation of propene by the cyclopentadienyl-amide titanium catalyst systems [η5,η1-C5H4(CH2)2NR]TiCl2/MAO and [η5,η1-C5H4(CH2)2NR]Ti(CH2Ph)2/B(C6F5)3 (R = tBu, iPr, Me), the catalyst with the smallest substituent (Me) on the amido moiety consistently gives the highest polymer molecular weight. This differs from the trend usually observed in related catalysts with tetramethylcyclopentadienyl-amide ancillary ligands, where larger amide substituents result in higher molecular weights. Based on the present information a hypothesis is formulated in which an increased cation-anion interaction for the less sterically hindered catalyst is responsible for disfavouring chain transfer relative to chain growth.

Total syntheses of conformationally-locked difluorinated pentopyranose analogues and a pentopyranosyl phosphate mimetic

Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate

Structural variation, dynamics, and catalytic application of palladium(II) complexes of di-N-heterocyclic carbene-amine ligands

A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(k(2)-(CN)-C-tBu(Bn)CN(Bn)C-tBu)PdCl2] (12) and [trans-(kappa(2)-(CN)-C-Mes(H)C-Mes)PdCl2] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between - 40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C-s symmetry and for 13 rotation of the mesityl groups is prevented. In the related C-1 complex [(kappa(3)-(CN)-C-tBu(H)C-tBu)PdCl][CI] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12 - 14 and two equivalents of AgBF4 in acetonitrile gives the analogous complexes [trans-(kappa(2)-(CN)-C-tBu(Bn)C-tBu)PdCl2] (12) and [trans-(kappa(CN)-C-2Mes(H)C-Mes)PdCl2] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 ans 25 degrees C shows the di-NHC-amine ligand is flexible expressing C-s symmetry and for 13 rotation of the mesityl groups is prevented. In the related C-1 complex [kappa(3)-(CN)-C-tBu(H)C-tBu)PdCI][CI] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C.Reaction between 12-14 and two equivalents of AgBF4 in acetonitrile gives the analogous complexes [trans-(kappa(2)-(CN)-C-tBu(H)(CPd)-Pd-tBu(MeCN)(2)][BF4](2) (15), [trans-(kappa(CN)-C-2Mes(H)C-Mes)Pd(MeCN)(2)[BF4](2 (16)) and [(kappa(3)-(CN)-C-tBu(H)C-tBu)Pd(MeCN)][BF4](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors C-tBu(H)N(Bn)C(H) (tBu)][CI](2) (2) and [C-tBu(H) N(H)C(H)(tBu)][BPh4](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively

Fragmentable Heterogeneous Cocatalysts for the Metallocene-Catalyzed Polymerization of Olefins, II [1]. Preparation, Characterization and Testing of the Cocatalysts and Microscopic Evaluation of the Polyethylene

Surface modified silica were reacted with different aluminiumalkyls AlR2R’ (R = Me, Et, i-Bu, R’ = H, Me, Et, i-Bu), oligomeric methylaluminoxane (MAO) and combinations of both, to yield heterogeneous cocatalysts. These cocatalyts were employed to polymerize ethylene using zirconocene dichloride as the catalyst. The polymerization activity profiles have been recorded and compared with the information gained from the scanning electron microscopy (SEM) images of the polymers. The fragmentation of the heterogeneous cocatalyts upon polymerization has been demonstrated. The degree of fragmentation and the polymerization activity depend on the preparation of the silica supports and on the preparation of the heterogeneous cocatalysts using these supports. The most reactive, fragmentable heterogeneous cocatalysts show polymerization activities slightly higher than MAO in homogeneous solution and almost 1.5 times higher than commercially available MAO on silica (=MAO on Sylopol).BMBF, 03C0295, Verbundprojekt: Heterogene und homogene Cokatalysatoren und Katalysatoren für die OlefinpolymerisationDFG, GRK 352, Synthetische, mechanistische und reaktionstechnische Aspekte von Metallkatalysatore

Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts

Bisphenolate ligands with pyridine- and benzene-diyl linkers have been synthesized and metalated with group 4 and 5 transition metals. The solid-state structures of some of the group 4 complexes have been solved. The titanium, zirconium, hafnium, and vanadium complexes were tested for propylene polymerization and ethylene/1-octene copolymerization activities with methylaluminoxane as cocatalyst. The vanadium(III) precatalyst is the most active for propylene polymerization and shows the highest 1-octene incorporation for ethylene/1-octene copolymerization. The zirconium(IV) precatalyst was the most active for propylene polymerization of the group 4 precatalysts. Titanium(IV) and zirconium(IV) precatalysts with pyridine-diyl linkers provided mixtures of isotactic and atactic polypropylene while titanium(IV) precatalysts with benzene-diyl linkers gave atactic polypropylene only. The hafnium(IV) precatalyst with a pyridine-diyl linker generated moderately isotactic polypropylene

2-{2,6-Bis[bis(4-fluorophenyl)methyl]-4-chlorophenylimino} -3-aryliminobutylnickel(II) bromide complexes: Synthesis, characterization, and investigation of their catalytic behavior

The series of 2-{2,6-bis[di(4-fluorophenyl)methyl]-4-chlorophenylimino}-3- aryliminobutane derivatives (L1-L5) and their nickel(II) dibromide complexes (Ni1-Ni5) were synthesized, and all organic compounds were fully characterized by the Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy and by elemental analysis, while the nickel complexes were characterized by FT-IR spectroscopy, elemental analysis, as well as by single-crystal X-ray diffraction for two representative examples, namely Ni1 and Ni4. A distorted tetrahedral geometry was observed for these four-coordinate nickel complexes. Upon the activation with either Methylaluminoxane or modified methylaluminoxane as co-catalyst, all nickel complex precatalysts showed very high activity toward ethylene polymerization with activities of up to 10 7 g(PE)·mol -1 (Ni)·h -1 , and afforded highly branched polyethylene with a bimodal distribution. © 2014 Elsevier B.V

Initiation of Olefin Metathesis: Reaction of Deca-2,8-diene with Catalysts formed from Me_4Sn-WC1_6 and Me_3Al_2Cl_3-(Ph_3P)_2(NO)_2Cl_2Mo

The initial product of the metathesis of deca-2,8-diene with metathesis catalysts formed from either Me_4Sn–WCl_6 or Me_3Al_2Cl_3–(Ph_3P)_2(NO)_2Cl_2Mo is propene; labelling of the terminal groups of the diene and the alkylating agents gives a labelling pattern in the propene that is best explained in terms of generation of a carbene in the initiation step from the alkylating agent