, Cq-Flu), vol.8, pp.103-110
, mL of a 2.5 M solution in hexane, 2.45 mmol), and HfCl 4 (0.380 g, 1.23 mmol). The compound was recovered as an orange-yellow powder (0.520 g, 0.38 mmol, 62%). 1 H NMR (toluene-d 8, Using a protocol similar to that described above for 3a-Zr, compound 3a-Hf was prepared from 1,4-bis(cyclopenta-2,4-dien-1-yl(3,6-di-tert-butyl-fluoren-9-yl)ethyl)benzene (0.500 g, 0.61 mmol)
,
Anal. calcd for C 62 H 66 ,
, Using a protocol similar to that described above for 3a-Zr, compound 3b-Zr was prepared from 2b (0.660 g, 0.84 mmol), n-BuLi (1.37 mL of a 2.0 M solution in hexane, 3.37 mmol), and ZrCl 4 (0.392 g, 1.68 mmol). The compound was isolated as a red powder
, 7.98 (s, 4H, CH-Ph), 7.67 (m, 4H, CH-Flu), vol.7, p.27
, 64 (s, 2H, CH-ansa), 6.36 (dq, 3 J = 2.5, 4H, CH-Cp), 5.84 (dq, 3 J = 2.5, 4H, CH-Cp), 1.47 (d, 36H, CH 3 -t Bu). 13 C NMR (CD 2 Cl 2 , 125 MHz, 25 ? C): ? 150, 120.3 (Cq), 119.6 (CH-Flu), 119.6 (CH-Cp), 119.5 (CH-Cp), vol.6
, Cp)ZrCl, vol.2, p.3
, Using a protocol similar to that described above for 3a-Zr, compound 3c-Zr was prepared from 2c (0.520 g, 0.64 mmol), n-BuLi (1.0 mL of a 2.5 M solution in hexane, 2.55 mmol), and ZrCl 4 (0.300 g, 1.27 mmol). The product was isolated as a red powder
, MHz, 25 ? C): ? 8.43-8.23 (m, 4H, CH-Flu), 8.05 (m, 2H, CH-Flu), 7.70 (dt, J = 7.8, 1.4, 1H, CH-Flu), 7.63-7.25 (m, 6H, CH-Flu + CH-Ph), 7.06-6.90 (m, 2H, CH-Ph), 6.47 (d, J = 9.1, 1H, CH-Ph), 6.28-6.23 (m, 1H, CH-Flu), 6.23-6.15 (m, 1H, CH-Cp), 6.13-6.04 (m, 1H, CH-Cp), 5.90-5.84 (m, 1H, CH-Cp), 5.74 (m, 1H, CH-Cp), 5.67-5.57 (m, 2H, CH-Cp), 5.55-5.36 (m, 1H, CH-Cp), 5.14 (d, J = 2.7, 1H, CH-Cp), 2.55-2.13 (m, 6H, CH 3
, {Ph(Me)C-(3,6-tBu 2 Flu)(Cp)}ZrCl 2 (3a'-Zr), vol.16
, The compound was isolated as a red powder (0.410 g, 0.67 mmol, 76%). 1 H NMR (toluene-d 8 , 500 MHz, 25 ? C): ? 8.07 (ddd, J = 7.0, 1.9, 0.7, 2H, CH-Flu), 7.43 (dt, J = 7.8, 1.7, 1H, CH-Ph), vol.7
, Using a protocol similar to that described above for 3a-Zr, compound 3b'-Zr was prepared from 2b' (0.430 g, 0.99 mmol), n-BuLi (0.81 mL of a 2.5 M solution in hexane, 1.99 mmol), and ZrCl 4 (0.230 g, 0.99 mmol). The product was isolated as a red powder (0.540 g, 0.86 mmol, 87%), vol.8, pp.558-573, 2018.
, CH-Flu), 6.17-6.05 (m, 2H, CH-Flu), 5.80 (s, 1H, CH), 5.48 (t, J = 2.8, 1H, CH-Cp), 5.29 (t, J = 2.8, 1H, CH-Cp), 1.39 (s, 18H, MHz, 25 ? C): ? 8.24 (s, 2H, CH-Flu), 7.55 (d, J = 7.4, 2H, CH-Ph), 7.42 (d, J = 9.0, 1H, CH-Ph), 7.24 (m, 3H, CH-Ph), 6.99 (d, J = 8.8, 1H, CH-Flu), 6.92 (d, J = 9.1, 1H, CH-Flu), 6.51 (d, J = 9, vol.0, p.105
, The product was isolated as an orange powder (0.076 g, 0.86 mmol, 56%). 1 H NMR (C 6 D 6 , 500 MHz, 25 ? C): ? 8.22 (dt, J = 9, Cp)}HfCl 2 (3b'-Hf) This compound was prepared as described above for 3a starting from 2b' (0.090 g, 0.20 mmol), n-BuLi (0.16 mL of a 2.5 M solution in hexane, 0.41 mmol), and HfCl 4 (0.060 g, 0.2 mmol), vol.18
, , vol.3
Anal. calcd. for C 33 H 34 Cl 2 Hf (680.1503): C 58, vol.29 ,
, Ethylene Homopolymerization and Ethylene/1-hexene Copolymerization Polymerization experiments were performed in a 300 mL high-pressure glass reactor equipped with a mechanical stirrer (Pelton turbine) and externally heated with a double mantle with a circulating water bath. The reactor was filled with toluene (100 mL, p.1
, The reactor was thermally equilibrated at the desired temperature for 30 min, the ethylene pressure was decreased to 1 bar, and a solution of the catalyst precursor in toluene (ca. 2 mL) was added by syringe. The ethylene pressure was immediately increased to 5.5 bar (kept constant with a back regulator), and the solution was stirred for the desired time (typically 15 min). The temperature inside the reactor (typically 60 ? C) was monitored using a thermocouple. The polymerization was stopped by venting the vessel and quenching with a 10% HCl solution in methanol (ca. 2 mL). The polymer was precipitated in methanol (ca. 200 mL), and 35% aqueous HCl (ca. 1 mL) was added to dissolve possible catalyst residues. The polymer was collected by filtration, mL of a 30 wt-% solution in toluene) and pressurized at 5.5 bar of ethylene (Air Liquide, 99.99%)
, Crystal Structure Determination of 3a'-Zr Diffraction data were collected at 150 K using a Bruker APEX CCD diffractometer, 2018.
Multinuclear Olefin Polymerization Catalysts, Chem. Rev, vol.111, pp.2450-2485, 2011. ,
Multinuclear Group 4 Catalysis: Olefin Polymerization Pathways Modified by Strong Metal-Metal Cooperative Effects, Acc. Chem. Res, vol.47, pp.2545-2557, 2014. ,
Biphenylene-Bridged Dinuclear Group 4 Metal Complexes: Enhanced Polymerization Properties in Olefin Polymerization, Organometallics, vol.24, pp.3618-3620, 2005. ,
Synthesis of a dinuclear ansa-zirconocene catalyst having a biphenyl bridge and application to ethene polymerization, J. Mol. Catal. A Chem, vol.128, pp.273-278, 1998. ,
Catalytic Trimerization of Ethene with Highly Active Cyclopentadienyl?Arene Titanium Catalysts, Organometallics, vol.21, pp.5122-5135, 2002. ,
Copolymerization characteristics of homogeneous and in situ supported, J. Mol. Catal. A Chem, vol.194, pp.19-28, 2003. ,
Syntheses of polymethylene bridged dinuclear zirconocenes and investigation of their polymerisation activities, J. Organomet. Chem, vol.580, pp.90-97, 1999. ,
Preparation of syndiotactic polystyrene using the doubly bridged dinuclear titanocenes, Eur. Polym. J, vol.40, pp.227-235, 2004. ,
Zr/Zr and Zr/Fe Dinuclear Complexes with Flexible Bridging Ligands. Preparation by Olefin Metathesis Reaction of the Mononuclear Precursors and Properties as Polymerization Catalysts, Organometallics, vol.24, pp.2705-2712, 2005. ,
Binuclear titanocenes linked by the bridge combination of rigid and flexible segment: Synthesis and their use as catalysts for ethylene polymerization, J. Mol. Catal. A Chem, vol.267, pp.86-91, 2007. ,
Significant Proximity and Cocatalyst Effects in Binuclear Catalysis for Olefin Polymerization, Macromolecules, vol.38, pp.9015-9027, 2005. ,
Catalyst/Cocatalyst Nuclearity Effects in Single-Site Polymerization. Enhanced Polyethylene Branching and ?-Olefin Comonomer Enchainment in Polymerizations Mediated by Binuclear Catalysts and Cocatalysts via a New Enchainment Pathway, J. Am. Chem. Soc, vol.124, pp.12725-12741, 2002. ,
Catalyst Nuclearity Effects in Olefin Polymerization. Enhanced Activity and Comonomer Enchainment in Ethylene + Olefin Copolymerizations Mediated by Bimetallic Group 4 Phenoxyiminato Catalysts, Macromolecules, vol.42, 1920. ,
New bridged zirconocenes for olefin polymerization: Binuclear and hybrid structures, J. Mol. Catal. A Chem, vol.128, pp.279-287, 1998. ,
Synthesis, Characterization, and Marked Polymerization Selectivity Characteristics of Binuclear Phenoxyiminato Organozirconium Catalysts, J. Am. Chem. Soc, vol.130, pp.12-13, 2008. ,
Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), J. Organomet. Chem, vol.518, pp.1-6, 1996. ,
Polymerizations of ethylene and styrene initiated with trisiloxane-bridged dinuclear titanium metallocene/MMAO catalyst systems, Macromol. Rapid Commun, vol.16, pp.265-268, 1995. ,
Preparation of new dinuclear half-titanocene complexes with ortho-and meta-xylene linkages and investigation of styrene polymerization, J. Organomet. Chem, vol.694, pp.3438-3443, 2009. ,
Synthesis and styrene polymerization properties of dinuclear half-titanocene complexes with xylene linkage, J. Organomet. Chem, vol.691, pp.5000-5006, 2006. ,
Ethylene polymerization by novel phenylenedimethylene bridged homobinuclear titanocene/MAO systems, Eur. Polym. J, vol.41, pp.1519-1524, 2005. ,
Fluorenyl complexes of zirconium and hafnium as catalysts for olefin polymerization, Chem. Soc. Rev, vol.27, pp.323-329, 1998. ,
From the lab bench to the plant: How to commercialize a metallocene catalyst?, Macromol. Chem. Symp, vol.173, pp.65-76, 2001. ,
Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts, Coord. Chem. Rev, vol.250, pp.155-169, 2006. ,
Effect of the Nature of Metallocene Complexes of Group IV Metals on Their Performance in Catalytic Ethylene and Propylene Polymerization, Chem. Rev, vol.100, pp.1205-1222, 2000. ,
Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts, Chem. Rev, vol.100, pp.1223-1252, 2000. ,
Selectivity in Propene Polymerization with Metallocene Catalysts, Chem. Rev, vol.100, pp.1253-1346, 2000. ,
Frontiers in Metal-Catalyzed Polymerization: Designer Metallocenes, Designs on New Monomers, Demystifying MAO, Metathesis Déshabillé, Chem. Rev, vol.100, pp.1167-1168, 2000. ,
Fluorenyl Containing Catalysts for Stereoselective Propylene Polymerization, Stereoselective Polymerization with Single Site Catalysts, 2000. ,
, New C1-Symmetric Ph2C-Bridged Multisubstituted ansa-Zirconocenes for Highly Isospecific Propylene Polymerization: Synthetic Approach via Activated Fulvenes, vol.29, pp.5073-5082, 2010.
URL : https://hal.archives-ouvertes.fr/hal-00576887
,
, -R 3 -5-Me-C 5 H 2 )}MCl 2 : Synthesis, Structure, Stereochemistry, and Use in Highly Isoselective Propylene Polymerization, Chiral-at-ansa-Bridged Group 4 Metallocene Complexes {, vol.30, pp.263-272, 2011.
2 )}ZrCl 2 : From Highly Isotactic Polypropylenes to Vinyl End-Capped Isotactic-Enriched Oligomers, Old and New C1-Symmetric Group 4 Metallocenes {, vol.32, pp.8375-8387, 2012. ,
URL : https://hal.archives-ouvertes.fr/hal-00813140
Are Solvent and Dispersion Effects Crucial in Olefin Polymerization DFT Calculations? Some Insights from Propylene Coordination and Insertion Reactions with Group 3 and 4 Metallocenes, ACS Catal, vol.5, pp.416-425, 2015. ,
URL : https://hal.archives-ouvertes.fr/hal-01969167
A Theoretical Outlook on the Stereoselectivity Origins of Isoselective Zirconocene Propylene Polymerization Catalysts, Chem. Eur. J, vol.24, pp.10784-10792, 2018. ,
URL : https://hal.archives-ouvertes.fr/hal-01807879
, Highly Soluble Olefin Polymerization Catalyst Activator. U.S. Patent, vol.20, p.90, 2009.
Nano-Linked Metallocene Catalyst Compositions and tHeir Polymer Products, European Patent WO, vol.2, 2009. ,
Method of Polymerizing an Olefin Using a Novel Transition Metal Compound, U.S. Patent, vol.5, 1995. ,
, J. Organomet. Chem, vol.553, pp.205-220, 1998.
Cooperative effects in binuclear zirconocenes: Their synthesis and use as catalyst in propene polymerization, J. Organomet. Chem, vol.460, pp.191-195, 1993. ,
Analysis of Metallocene using Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photo Ionization Coupled with Ion Mobility Mass Spectrometry, Proceedings of the 64th ASMS conference on Mass Spectrometry and Allied Topics, pp.5-9, 2016. ,
Comparison of Atmospheric Pressure Ionization for the Analysis of Heavy Petroleum Fractions with Ion Mobility-Mass Spectrometry, Energy Fuels, vol.30, pp.8896-8903, 2016. ,
URL : https://hal.archives-ouvertes.fr/hal-02046205
, Beware of Trimethylaluminum! Macromolecules, vol.42, pp.1789-1791, 2009.
An efficient catalytic method for fulvene synthesis, Tetrahedron, vol.67, pp.8607-8614, 2011. ,
SIR97: A new tool for crystal structure determination and refinement, J. Appl. Cryst, vol.32, pp.115-119, 1999. ,
A short history of SHELX, Acta Cryst, vol.64, pp.112-122, 2008. ,
Electronic structure calculations on workstation computers: The program system turbomole, Chem. Phys. Lett, vol.162, pp.165-169, 1989. ,
Efficient molecular numerical integration schemes, J. Chem. Phys, vol.102, pp.346-354, 1995. ,
Auxiliary basis sets to approximate coulomb potentials, Chem. Phys. Lett, vol.242, pp.652-660, 1995. ,
, TURBOMOLE GmbH, 1989.
Fast evaluation of the coulomb potential for electron densities using multipole accelerated resolution of identity approximation, J. Chem. Phys, vol.118, pp.9136-9148, 2003. ,
Nuclear second analytical derivative calculations using auxiliary basis set expansions, Chem. Phys. Lett, vol.384, pp.103-107, 2004. ,
Fully optimized contracted gaussian basis sets of triple zeta valence quality for atoms Li to Kr, J. Chem. Phys, vol.100, pp.5829-5835, 1994. ,