Catalyst systems based on carbonylamino fulvenes

Information

  • Patent Grant
  • 8436115
  • Patent Number
    8,436,115
  • Date Filed
    Wednesday, July 16, 2008
    16 years ago
  • Date Issued
    Tuesday, May 7, 2013
    11 years ago
Abstract
The present invention discloses metallic complexes based on carbonylamino fulvene ligands; their method of preparation and their use in the oligomerisation or polymerisation of ethylene and alpha-olefins.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of PCT/EP2008/059282, filed Jul. 16, 2008, which claims priority from EP 07290931.0, filed Jul. 24, 2007.


The present invention discloses catalyst components based on carbonylamino fulvene ligands their method of preparation and their use in the polymerisation of ethylene and alpha-olefins.


Several ligands have been described in literature, some of which were tested in complexation with metals but none of them have been used as catalysts for the polymerisation of ethylene or alpha-olefins. Some ligands are described for example in Lloyd and Preston (D. Lloyd, N. W. Preston, J. Chem. Soc. C, 1969, 2464-2469.) or by Linn and Sharkey (W. J. Linn, W. G. Sharkey J. Am. Chem. Soc. 1957, 79, 4970-2.) or in Snyder et al. (C. A. Snyder, J. P. Selegue, N. C. Tice, C. E. Wallace. M. T. Blankenbuehler, S. Parkin, K. D. E. Allen, R. T. Beck, J. Am. Chem. Soc. 2005, 127, 15010-11.) or in Dong et al. (Y. B. Dong, Y. Geng, J. P. Ma and R. Q. Huang, Inorg. Chem. 2005, 44, 1693-1703.)


There is a need to develop new catalyst system having good activity and able to produce polymers tailored to specific needs.


It is an aim of the present invention to prepare new catalyst components that can be used in the polymerisation of ethylene and alpha-olefins.


It is also an aim of the present invention to provide very active catalyst components.


It is another aim of the present invention to provide a method for polymerising or copolymerising ethylene and alpha-olefins.


The present invention reaches, at least partially, any one of those aims.


Accordingly, the present invention discloses a method for preparing a metallic complex that comprises the steps of:

    • a) preparing a carbonylamino fulvene ligand by condensation reaction of an hydroxycarbonyl fulvene ligand with a primary amine, in a polar solvent and with an acid catalyst




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      • wherein R1 and R2 are the same or different and are selected from alkyl, aryl, alkylaryl, arylalkyl having at most 20 carbon atoms or heteroatoms-containing groups;



    • b) providing a metallic precursor MZn wherein M is a metal Group 6 to 11 of the Periodic Table, Z is a negative counter-anion and n is the valence of M;

    • c) complexing the metallic precursor of step b) with the carbonylamino fulvene of step a);

    • d) retrieving a metallic complex.





Preferably, both R1 are the same and are selected from alkyl, unsubstituted or substituted phenyl (Ph), CHPh2 wherein Ph may be substituted or not, or the R1 groups include heteroatom(s)-containing units. More preferably R is CHPh2 or cyclohexyl or paramethoxyphenyl. Most preferably R1 is CHPh2.


Preferably R2 is CH2pyridine or includes heteroatoms-containing units. More preferably R2 is CH2pyridine or furan.


Preferred embodiments according to the present invention are characterised by the following pairs:

  • Both R1 are CHPh2 and R2 is CH2pyridine,
  • Both R1 are paramethoxyphenyl and R2 is CH2pyridine,
  • Both R1 are cyclohexyl and R2 is furan.


Most preferably, both R1 are CHPh2 and R2 is CH2pyridine.


Preferably, M is CrII, CrIII or Ni, more preferably, it is CrII.


Preferably Z is halogen or acetate, more preferably, it is Cl.


The preferred polar solvent is ethanol and the preferred acid catalyst is paratoluene sulfonic acid.


Several types of metallic complexes can be formed, one where the metal is coordinated to one ligand and one where the metal is coordinated to two ligands. The relative amounts of each ligand and metal unit depend upon the nature of ligand and of the metal. The amount of ligand must therefore be of at least one equivalent of ligand per metallic equivalent. In a preferred embodiment according to the present invention, the metal is CrII and it is coordinated to one ligand or two ligands.


The present invention further discloses an active catalyst system comprising the metallic complex and an activating agent having an ionising action.


Suitable activating agents are well known in the art. The activating agent can be an aluminium alkyl represented by formula AIR+nX3−nwherein R+ is an alkyl having from 1 to 20 carbon atoms and X is a halogen. The preferred alkylating agents are triisobutyl aluminium (TIBAL) or triethyl aluminium (TEAL).


Alternatively and preferably, it is an aluminoxane and comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by formula




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for oligomeric, linear aluminoxanes and by formula




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for oligomeric, cyclic aluminoxane,


wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R* is a C1-C8 alkyl group and preferably methyl.


The amount of activating is selected to give an AI/M ratio of from 100 to 3000, preferably of about 1000.


Suitable boron-containing activating agents may comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L′−H]+[B Ar1 Ar2 X3 X4]—as described in EP-A-0277004 (page 6, line 30 to page 7, line 7). The amount of boron-containing activating agent is selected to give B/M ratio of from 0.5 to 5, preferably of about 1.


The preferred activating agent is methylaluminoxane (MAO).


In another embodiment, according to the present invention, the metallic complex may be deposited on a conventional support impregnated with an activating agent.


Preferably, the conventional support is silica impregnated with methylaluminoxane (MAO). Alternatively, it can be an activating support such as fluorinated alumina silica.


The present invention further discloses a method for preparing an active catalyst system that comprises the steps of:

    • a) providing a carbonylamino fulvene ligand;
    • b) complexing the ligand of step a) with a metallic salt MZn in a solvent with an acid catalyst;
    • c) retrieving a catalyst component;
    • d) optionally depositing the catalyst component of step c) on a support;
    • e) activating the catalyst component of step c) or step d) with an activating agent having an ionising action;
    • f) optionally adding a scavenger;
    • g) retrieving an active oligomerisation or polymerisation catalyst system.


Alternatively, in step d), the catalyst component is deposited on a support impregnated with an activating agent or on an activating support. In that case, the activating step e) is not necessary.


The scavenger may be selected from triethylaluminium, triisobutylaluminum, tris-n-octylaluminium, tetraisobutyldialuminoxane or diethyl zinc.


The active catalyst system is used in the oligomerisation and in the polymerisation of ethylene and alpha-olefins.


The present invention discloses a method for the oligomerisation or the homo- or co-polymerisation of ethylene and alpha-olefins that comprises the steps of:

    • a) injecting the active catalyst system into the reactor;
    • b) injecting the monomer and optional comonomer;
    • c) maintaining under polymerisation conditions;
    • d) retrieving the oligomers and/or polymer.


The pressure in the reactor can vary from 0.5 to 60 bars, preferably from 15 to 45 bars. The productivity of the catalyst system increases with increasing pressure.


The polymerisation temperature can range from 10 to 100° C., preferably from 25 to 55° C. The productivity of the catalyst system decreases with increasing temperature.


Preferably the monomer and optional comonomer are selected from ethylene, propylene or 1-hexene.


The present invention also discloses the polymers obtained with the new catalyst systems.





LIST OF FIGURES


FIG. 1 represents the molecular structure of ligand D obtained by X-Ray.



FIG. 2 represents examples of ligands prepared according to the present invention.



FIG. 3 represents the molecular structure of the metallic compound resulting from the complexation of CrCl2 with ligand L.





EXAMPLES
Synthesis of Ligands

The ligands were prepared following methods similar to those described for example in Lloyd and Preston (D. Lloyd, N. W. Preston, J. Chem. Soc. C, 2464-2469, 1969.)


All reactives were purchased from commercially available sources and used without purification and the solvents were purified following standard procedures. The NMR spectra were recorded either on a Brücker ARX 200 spectrometer, at 200 MHz for 1H spectra and at 50 MHz for 13C spectra, or on a Brücker AC 300P at 300 MHz for 1H spectra and at 75 MHz for 13C spectra. Mass spectras were obtained with a high resolution mass spectrometer Varian MAT 311 and microanalyses were carried out on a Flash EA1112 CHNS/O Thermo Electron (Centre Regional de Mesures des Physiques de l'Ouest, Rennes, France). Crystallographic data collection, unit cell constant and space group determination were carried out on an automatic ‘Enraf Nonius FR590’ NONIUS Kappa CCD diffractometer with graphite monochromatised Mo—Kα radiation at 120 K. The cell parameters are obtained with Denzo and Scalepack with 10 frames (psi rotation: 1° per frame). The structure was solved with SIR-97. The whole structure was refined with SHELXL97 by the full-matrix least-square techniques.


Parallel Synthesis of Carbonylamino Fulvene Ligands.


Carbonylamino fulvene ligands A, B, C, D, . . . U were synthesised in parallel with a Büchi Syncore. In each tube, 0.2 to 0.6 mmol of hydroxycarbonyl fulvene were introduced with 1.1 equivalents of amine, 0.5 mg of paratoluene-sulfonic acid (PTSA) and 20 ml of ethanol.




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The mixtures were heated for a period of time of 12 h at a temperature of 80° C. Ligands A, B, C, J, K and L were heated for 12 additional hours at a temperature of 110° C. Ligands D and H were crystallised from ethanol. Otherwise, the solvent was evaporated under vacuum for 1 night and crude products were purified by column chromatography on silica gel and dried over MgSO4 to afford new carbonylamino fulvene ligands. Several ligands synthetised according to the present invention are displayed in FIG. 2. The results for different amines are displayed in TABLE I for benzylamine; in TABLE II for furfurylamine and in TABLE III for picolylamine.









TABLE I





Synthesis with benzylamine.





















R1=


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
286.41   165.6   0.578
274.31   168.2   0.613
386.53   218.5   0.565
454.56   109.7   0.241







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V amine (μL) n amine (mmol)
69 0.636
74 0.674
68 0.622
29 0.265







A
D
G
J



Purification
EtOAc/C7
EtOAc/C7
recristallisation
DCM/C7




1/1
1/1
EtOH
2/1







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M carbonylaminofulvene (g/mol) m carbonylaminofulvene (mg) n carbonylaminofulvene (mmol)
375.56   144   0.383
363.46   200   0.550
475.68   230   0.484
543.71   68   0.125






Yield (%)
66
90
86
52

















R1=


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
334.37   200.0   0.598
454.16   167.6   0.369
254.24   105.1   0.413








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V amine (μL) n amine (mmol)
72 0.658
44 0.406
50 0.455








M
P
S




Purification
recristallisation
EtOAc/C7
EtOAc/C7





EtOH
1/1
1/1








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M carbonylaminofulvene (g/mol) m carbonylaminofulvene (mg) n carbonylaminofulvene (mmol)
423.52   208   0.491
543.31   108   0.199
343.39   136   0.396







Yield (%)
82
54
96





EtOAc = ethyl acetate, DCM = dichloromethane, C7 = heptane, EtOH = ethanol













TABLE II





Synthesis with furfurylamine





















R1 =


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
286.41   164.0   0.573
274.31   161.8   0.590
386.53   221.7   0.574
454.56   108.6   0.239







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V amine (μL) n amine (mmol)
69 0.630
71 0.649
69 0.631
29 0.263







B
E
H
K



Purification
EtOAc/C7
EtOAc/C7
EtOAc/C7
DCM/C7




1/1
1/1
1/1
2/1







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M carbonylaminofulvene (g/mol) m carbonylaminofulvene (mg) n carbonylaminofulvene (mmol)
365.53   178.0   0.487
353.43   195.0   0.552
465.65   206.0   0.442
533.68   93.0   0.174






Yield (%)
85
94
77
73

















R1 =


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
334.37   168.2   0.503
454.16   168.2   0.370
254.24   120.6   0.474








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V amine (μL) n amine (mmol)
49 0.553
44 0.407
57 0.522








N
Q
T




Purification
EtOAc/C7
EtOAc/C7
EtOAc/C7





1/1
1/1
1/1








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M carbonylaminofulvene (g/mol) m carbonylaminofulvene (mg) n carbonylaminofulvene (mmol)
413.49   76.0   0.183
533.28   108.0   0.203
333.36   153.0   0.459







Yield (%)
36
55
97





EtOAc = ethyl acetate, DCM = dichloromethane, C7 = heptane, EtOH = ethanol













TABLE III





Synthesis with 2-picolylamine





















R1=


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
286.41   174.7   0.610
274.31   158.1   0.576
386.53   223.7   0.579
454.56   205.6   0.452







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V amine (μL) n amine (mmol)
73 0.671
69 0.634
70 0.637
54 0.498







C
F
I
L



Purification
EtOAc/C7
EtOAc/C7
EtOAc/C7
Ether/C7




1/1
1/1
1/1
1/1







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M carbonylaminofulvene (g/mol) m carbonylarninofulvenen (mg) n carbonylaminofulvene (mmol)
376.55   187   0.497
364.45   193   0.530
476.67   187   0.392
544.70   174   0.319






Yield (%)
81
92
68
71

















R1=


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M hydroxycarbonylfulvene (g/mol) m hydroxycarbonylfulvene (mg) n hydroxycarbonylfulvene (mmol)
334.37   170.3   0.509
454.16   161.8   0.356
254.24   114.3   0.450








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V amine (μL) n amine (mmol)
61 0.560
43 0.392
54 0.495








O
R
U




Purification
EtOAc/C7
EtOAc/C7
EtOAc/C7





2/1
2/1
1/1








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M carbonylaminofulvene (g/mol) m carbonylarninofulvenen (mg) n carbonylaminofulvene (mmol)
424.51   129   0.304
544.30   109   0.200
344.38   93   0.270







Yield (%)
60
56
60





EtOAc = ethyl acetate, DCM = dichloromethane, C7 = heptane, EtOH = ethanol






Ligand A: 1-(cyclohexanoyl)-6-benzylamino-6-cyclohexyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.87 (1H, s, N16H), 7.31 (2H, d, J=0.03 Hz, C2H and C4H), 7.21 (5H, m, C19H, C2OH and C21H), 6.19 (1H, s, C3H), 4.63 (2H, d, J=0.23 Hz, C17H), 3.44-2.75 (2H, m, C12H and C7H), 1.83-0.97 (20H, m, C8H, C9H, C10H, C13H, C14H, C15H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 199.23 (C11), 173.58 (C6), 137.93 (C18), 131.82 (C2), 130.60 (C4), 128.84 (C20), 127.67 (C21), 127.14 (C19), 123.97 (C1), 117.01 (C5), 116.03 (C3), 47.87 (C17), 47.04 (C12), 42.03 (C15), 32.26 (C8), 31.06 (C10), 26.99 (C13), 26.32 (C14), 26.21 (C9), 25.85 (C7).


HRMS: Calcd. for M+. (C26H33NO) m/z=375.25621. found 375.2571 (2 ppm).


Anal. Cald for C26H33NO: C, 83.15; H, 8.86; N, 3.73, O, 4.26. found C, 82.71; H, 8.91; N, 4.00.


Ligand B: 1-(cyclohexanoyl)-6-(furan-2-yl methyl)amino-6-cyclohexyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.92 (1H, s, N16H), 7.56 (1H, d, J=0.02 Hz, C21H) 7.43 (2H, d, J=0.025 Hz, C2H and C4H), 7.28 (1H, m, C20H), 6.34-6.40 (2H, m, C3H and C19H), 4.78 (2H, d, J=0.24 Hz, C17H), 3.52-3.09 (2H, m, C12H and C7H), 2.19-1.31 (20H, m, C8H, C9H, C10H, C13H, C14H, C15H−



13C NMR (CDCl3, 50 MHz, ppm) δ: 199.11 (C11), 173.22 (C6), 150.40 (C18), 142.43 (C21), 132.02 (C2), 130.83 (C4), 124.01 (C1), 117.06 (C5), 116.12 (C3), 110.68 (C20), 107.90 (C19), 46.93 (C7), 41.74 (C10), 40.95 (C17), 32.44 (C13), 30.98 (C15), 27.00 (C8), 26.28 (C9), 26.17 (C14), 25.87 (C12).


HRMS: Calcd. for M+. (C24H31NO2) m/z=365.23548. found 365.2344 (2 ppm).


Anal. Cald for C24H31NO2: C, 78.86; H, 8.55; N, 3.83, O, 8.75. found C, 78.54; H, 8.60; N, 3.89.


Ligand C: 1-(cyclohexanoyl)-6-(pyridine-2-methyl)amino-6-cyclohexyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 15.01 (1H, s, N16H), 8.59 (1H, d, J=0.01 Hz, C22H), 7.68 (1H, t, J=0.025 Hz, C20H), 7.45-7.51 (2H, m, C2H and C4H), 7.36 (1H, s, C19H), 7.22 (1H, t, J=0.02 Hz, C21H), 6.34 (1H, t, J=0.02 Hz, C3H), 4.92 (2H, d, J=0.26 Hz, C17H), 3.60-2.95 (2H, m, C12H and C7H), 1.96-1.31 (20H, m, C8H, C9H, C10H−C13H, C14H, C15H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 199.72 (C11), 173.84 (C6), 157.76 (C18), 149.35 (C22), 137.09 (C19), 135.48 (C20), 132.15 (C2), 130.88 (C4), 124.03 (C1), 122.59 (C21), 117.06 (C5), 116.28 (C3), 49.88 (C17), 46.95 (C7), 41.86 (C10), 32.38 (C13), 31.02 (C15), 26.82 (C8), 26.26 (C9), 26.17 (C14), 25.76 (C12).


HRMS: Calcd. for M+. (C25H32N2O) m/z=376.25146. found 376.2503 (3 ppm).


Anal. Cald for C25H32N2O: C, 79.75; H, 8.57; N, 7.44, O, 4.25. found C, 79.34; H, 8.67; N, 7.27.


Ligand D: 1-benzoyl-6-benzylamino-6-phenyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 15.28 (1H, s, N16H), 7.51 (2H, m, C13H), 7.20-6.88 (13H, m, C8H, C9H, C10H, C14H, C15H, C19H, C20H, C21H), 6.74 (1H, m, C2H), 5.96 (1H, m, C4H), 5.75 (1H, t, J=0.02 Hz, C3H), 3.68 (2H, d, J=0.03 Hz, C17H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.13 (C11), 166.39 (C6), 142.42 (C12), 139.71 (C7), 137.05 (C18), 135.80 (C15), 134.04 (C10), 129.94 (C2), 129.72 (C4), 128.94 (C20), 128.92 (C13), 128.40 (C14), 128.32 (C9), 127.87 (C8), 127.82 (C21), 127.47 (C19), 125.35 (C1), 119.98 (C5), 118.20 (C3), 49.76 (C17).


HRMS: Calcd. for M+. (C26H21NO) m/z=363.16231. found 363.1594 (1 ppm).


Anal. Cald for C26H21NO: C, 85.92; H, 5.82; N, 3.85, O, 4.40. found C, 85.46; H, 6.06; N, 3.99.


Cristallography. Single crystals of compound D suitable for a single crystal X-ray determination were obtained by evaporation of a saturated solution in THF.















Empirical formula
C26 H21 N O


Formula weight
363.44


Temperature
120(2) K


Wavelength
0.71073 A


Crystal system, space group
Monoclinic, P 21/c


Unit cell dimensions
a = 6.22050(10) A alpha = 90 deg.



b = 17.5271(3) A beta = 91.6710(10) deg.



c = 18.2524(3) A gamma = 90 deg.


Volume
1989.16(6) A3


Z, Calculated density
4, 1.214 Mg/m3


Absorption coefficient
0.073 mm−1


F(000)
768


Crystal size
0.2 × 0.15 × 0.1 mm


Theta range for data collection
3.22 to 27.47 deg.


Limiting indices
−8 <= h <= 8, −22 <= k <=



22, −23 <= l <= 23


Reflections collected/unique
8885/4522 [R(int) = 0.0472]


Completeness to theta =
27.47 99.3%


Absorption correction
none


Refinement method
Full-matrix least-squares on F2


Data/restraints/parameters
4522/0/257


Goodness-of-fit on F{circumflex over ( )}2
1.078


Final R indices [I >
R1 = 0.0607, wR2 = 0.1598


2sigma(I)]



R indices (all data)
R1 = 0.0736, wR2 = 0.1702


Extinction coefficient
0.075(9)


Largest diff. peak and hole
0.337 and −0.271 e.A−3









The molecular structure of ligand D obtained by X-Ray is displayed in FIG. 1.


Ligand E: 1-benzoyl-6-(1-(furan-2-methyl)amino)-6-phenyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.36 (1H, s, N16H), 7.83 (2H, m, C13H), 7.59-7.50 (8H, m, C8H, C9H, C10H−C14H, C15H), 7.43 (1H, d, J=0.01 Hz, C2H), 7.20 (1H, m, C21H), 6.50 (1H, t, J=0.01 Hz, C20H), 6.37 (1H, m, C4H), 6.33-6.30 (2H, m, C3H and C19H), 4.49 (2H, d, J=0.02 Hz, C17H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.13 (C11), 166.07 (C6), 149.82 (C18), 142.82 (C21), 142.30 (C12), 139.99 (C7), 135.95 (C15), 133.85 (C10), 129.95 (C2), 129.77 (C4), 128.92 (C13), 128.53 (C14), 128.35 (C9), 127.84 (C8), 125.48 (C1), 119.92 (C5), 118.35 (C3), 110.64 (C20), 108.22 (C19), 42.93 (C17).


HRMS: Calcd. for M+. (C24H19NO2) m/z=353.14158. found 353.1417 (0 ppm).


Anal. Cald for C24H19NO2: C, 81.56; H, 5.42; N, 3.96, O, 9.05. found C, 80.35, H, 5.64; N, 4.13.


Ligand F: 1-benzoyl-6-(1-(pyridine-2-methyl)amino)-6-phenyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.49 (1H, s, N16H), 8.56 (1H, d, J=0.01 Hz, C22H), 7.80 (2H, m, C13H), 7.70 (1H, t, J=0.025 Hz, C20H), 7.54-7.42 (9H, m, C8H, C9H, C10H, C14H, C15H, and C19H), 7.22-7.17 (2H, m, C2H, C21H), 6.48 (1H, m, C4H), 6.28 (1H, t, J=0.02 Hz, C3H), 4.67 (2H, d, J=0.02 Hz, C17H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.14 (C11), 166.69 (C6), 156.79 (C18), 149.59 (C22), 142.27 (C7), 139.99 (C12), 137.13 (C20), 136.02 (C10), 133.89 (C15), 129.95 (C2), 129.72 (C4), 128.92 (C13), 128.31 (C14), 128.30 (C9), 127.81 (C8), 125.50 (C5), 122.60 (C19), 121.31 (C21), 119.97 (C1), 118.33 (C3), 51.41 (C17).


HRMS: Calcd. for M+. (C25H20N2O) m/z=364.15756. found 364.1557 (5 ppm).


Anal. Cald for: C, 82.39; H, 5.53; N, 7.69, O, 4.39. found C, 82.53; H, 5.56; N, 7.61.


Ligand G: 1-(4-tertbutylbenzoyl)-6-benzylamino-6-(4-tertbutylphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.32 (1H, s, N20H), 7.57 (2H, m, C15H), 7.40-7.13 (11H, m, C8H, C9H, C16H, C23H−C24H, C25H), 6.34 (1H, m, C2H), 6.11 (1H, m, C4H), 5.17 (1H, t, J=0.02 Hz, C3H), 4.38 (2H, d, J=0.02 Hz, C21H), 1.30 (18H, d, J=0.03 Hz, C12H3 and C19H3).



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.05 (C13), 166.71 (C6), 153.13 (C17), 152.84 (C10), 139.50 (C14), 139.28 (C7), 137.13 (C22), 135.51 (C2), 131.01 (C4), 128.87 (C24), 128.79 (C8), 128.20 (C9), 127.63 (C16), 127.44 (C16), 125.19 (C25), 125.07 (C23), 124.70 (C1), 119.92 (C5), 117.70 (C3), 49.68 (C21), 34.92 (C11 and C18), 31.35 (C12 and C19).


HRMS: Calcd. for M+. (C34H37NO) m/z=475.28752. found. 475.2899 (5 ppm)


Anal. Cald for C34H37NO: C, 85.85; H, 7.84; N, 2.94, O, 3.36. found C, 86.13; H, 7.99; N, 2.99.


Ligand H: 1-(4-tertbutylbenzoyl)-6-(1-(furan-2-methyl)amino)-6-(4-tertbutylphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.14 (1H, s, N20H), 7.56 (2H, d, J=0.03 Hz, C15H), 7.42-7.27 (6H, m, C8H−C9H, C16H), 7.23 (1H, s, C2H), 7.03 (1H, d′, J=0.01 Hz, C25H), 6.32 (1H, t, J=0.01 Hz, C24H), 6.18-6.09 (1H, m, C3H, C4H and C23H), 4.32 (2H, d, J=0.02 Hz, C21H), 1.26 (18H, d, J=0.03 Hz, C12H3 and C19H3)



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.09 (C13), 166.41 (C6), 153.17 (C17), 152.91 (C10), 149.98 (C22), 142.66 (C25), 139.62 (C14), 139.46 (C7), 135.72 (C2), 130.88 (C4), 128.93 (C8), 128.38 (C9), 125.39 (C16), 125.15 (C15), 124.71 (C1), 119.93 (C5), 117.92 (C3), 110.58 (C24), 108.08 (C23), 42.99 (C21), 34.88 (C11 and C18), 31.39 (C12 and C19).


HRMS: Calcd. for M+. (C32H35NO2) m/z=465.26678. found 465.2669 (0 ppm).


Anal. Cald for C32H35NO2: C, 82.54; H, 7.58; N, 3.01, O, 3.01. found C, 81.98; H, 7.57; N, 3.14.


Ligand I: 1-(4-tertbutylbenzoyl)-6-(1-(pyridine-2-methyl)amino)-6-(4-tertbutylphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.35 (1H, s, N20H), 8.37 (1H, m, C26H). 7.54 (2H, m, C15H), 7.48 (1H, d, C24H), 7.35-7.19 (7H, m, C8H−C9H, C16H, C2H), 7.05 (1H, m, C23H), 7.01 (1H, t, J=0.02 Hz, C25H), 6.34 (1H, m, C4H), 6.11 (1H, t, J=0.02 Hz, C3H), 4.52 (2H, d, J=0.02 Hz, C21H), 1.24 (18H, s, C12H3 and C19H3)



13C NMR (CDCl3, 50 MHz, ppm) δ: 191.07 (C13), 167.04 (C6), 157.02 (C26), 153.21 (C17), 152.85 (C10), 149.53 (C24), 139.70 (C7), 139.46 (C14), 137.12 (C23), 135.90 (C2), 130.93 (C4), 128.99 (C8), 128.21 (C9), 125.46 (C16), 125.16 (C15), 124.74 (C1), 122.50 (C22), 121.24 (C25), 120.06 (C5), 118.02 (C3), 51.47 (C21), 34.92 (C11 and C18), 31.39 (C12 and C19).


HRMS: Calcd. for M+. (C33H36N2O) m/z=476.28276. found 476.2830 (0 ppm).


Anal. Cald for C33H36N2O: C, 83.15; H, 7.61; N, 5.88, O, 3.36. found C, 82.65; H, 7.77; N, 5.81.


Ligand J: 1-(diphenylacetyl)-6-benzylamino-6-(diphenylmethyl)fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.95 (1H, s, N18H), 7.64 (1H, m, C2H), 7.38-7.10 (25H, m, C9H, C10H−C11H, C15H, C16H, C17H, C21H, C22H and C23H), 7.04 (1H, m, C4H), 6.31 (1H, s, C13H), 6.25-6.22 (2H, m, C3H and C7H,), 4.54 (2H, d, J=0.02 Hz, C19H).



13C NMR(CDCl3, 50 MHz, ppm) δ: 193.03 (C12), 167.51 (C6), 141.30 (C14), 138.85 (C8), 136.42 (C20), 134.93 (C2), 133.10 (C4), 129.27 (C16), 128.95 (C15), 128.92 (C10), 128.58 (C22), 128.39 (C9), 127.31 (C17), 126.96 (C21), 126.65 (C11), 125.92 (C1), 120.39 (C5), 117.60 (C3), 58.95 (C13), 52.10 (C19), 49.46 (C7).


HRMS: Calcd. for M+. (C40H33NO) m/z=543.25621. found 543.2539 (4 ppm).


Anal. Cald for C40H33NO: C, 88.36; H, 6.12; N, 2.58, O, 2.94. found C, 87.74; H, 6.07; N, 2.52.


Ligand K: 1-(diphenylacetyl)-6-(1-(furan-2-methyl)amino)-6-(diphenylmethyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.80 (1H, s, N18H), 7.64 (1H, m, C2H), 7.45-7.27 (21H, m, C9H, C10H, C11H, C15H, C16H, C17H and C23H), 7.07 (1H, m, C4H), 6.44 (1H, s, C13H), 6.32 (1H, m, C22H), 6.25 (1H, t, J=0.02 Hz, C3H), 6.19 (1H, s, C21H), 4.42 (2H, d, J=0.02 Hz, C19H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 192.99 (C12), 167.02 (C6), 149.35 (C20), 142.34 (C23), 141.27 (C14), 138.66 (C8), 135.22 (C2), 133.07 (C4), 129.27 (C16), 128.99 (C15), 128.93 (C10), 128.36 (C9), 127.36 (C17), 126.62 (C11), 126.01 (C1), 120.29 (C5), 117.74 (C3), 110.52 (C22), 107.87 (C21), 58.94 (C13), 52.10 (C19), 43.26 (C7).


HRMS: Calcd. for M+. (C38H31NO2) m/z=533.23548. found 533.2349 (1 ppm).


Anal. Cald for C38H31NO2: C, 85.52; H, 5.86; N, 2.62, O, 6.00. found C, 85.27; H, 5.95; N, 2.59.


Ligand L: 1-(diphenylacetyl)-6-(1-(pyridine-2-methyl)amino)-6-(diphenylmethyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.94 (1H, t, J=0.02 Hz, N18H,), 8.45 (1H, d, J=0.02 Hz C24H), 7.68 (1H, m, C2H), 7.50 (1H, t, J=0.03 Hz C22H), 7.46-7.27 (21H, m, C9H, C10H, C11H, C15H, C16H, C17H, C21H and C23H), 7.09 (1H, m, C4H), 6.39 (1H, s, C13H), 6.27 (1H, t, J=0.02 Hz, C3H), 6.25 (1H, s, C7H), 4.76 (2H, d, J=0.02 Hz, C19H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 193.22 (C12), 167.99 (C6), 156.45 (C24), 149.16 (C22), 141.25 (C14), 138.54 (C8), 136.60 (C21), 135.50 (C2), 133.42 (C4), 129.27 (C16), 129.00 (C15), 128.85 (C10), 128.42 (C9), 127.22 (C17), 126.68 (C11), 126.06 (C1), 122.20 (C22), 120.8 (C25), 120.38 (C5), 117.90 (C3), (C22), (C21), 59.03 (C13), 52.06 (C19), 51.17 (C7).


HRMS: Calcd. For M+. (C39H32N2O) m/z=544.25146. found 544.2533 (3 ppm).


Anal. Cald for C39H32N2O: C, 86.00; H, 5.92; N, 5.14, O, 2.94. found C, 86.08; H, 6.14; N, 4.80.


Ligand M: 1-(4-methoxybenzoyl)-6-(benzylamino)-6-(4-methoxyphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.26 (1H, s, N18H), 7.64 (2H, m, C14H), 7.22-7.12 (7H, m, C8H, C21H, C22H and C23H), 7.03 (1H, m, C2H), 6.90 (4H, m, C9H and C15H), 6.12 (1H, m, C4H), 3.77 (1H, t, J=0.02 Hz, C3H), 4.39 (2H, d, J=0.02 Hz, C19H), 3.78 (3H, s, C17H), 3.77 (3H, s, C11H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.41 (C12), 166.52 (C6), 161.26 (C16), 160.56 (C10), 138.87 (C20), 137.27 (C13), 135.20 (C2), 134.82 (C4), 131.06 (C15), 130.01 (C9), 128.81 (C22), 127.61 (C23), 127.28 (C21), 126.14 (C7), 125.19 (C1), 120.09 (C5), 117.59 (C3), 113.56 (C14), 113.06 (C8), 55.42 (C17), 55.40 (C11), 49.57 (C19).


HRMS: Calcd. for M+. (C28H25NO3) m/z=423.18344. found 423.1821 (3 ppm).


Anal. Cald for C28H25NO3: C, 79.41; H, 5.95; N, 3.31, O, 11.33. found C, 79.62; H, 5.95; N, 3.36.


Ligand N: 1-(4-methoxybenzoyl)-6-(1-(furan-2-methyl)amino)-6-(4methoxyphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.07 (1H, s, N18H), 7.63 (2H, d, J=0.04 Hz, C14H), 7.29 (2H, d, J=0.04 Hz, C8H), 7.27 (1H, m, C23H), 7.03 (1H, m, C2H), 6.92 (2H, d, J=0.04 Hz, C15H), 6.83 (2H, d, J=0.04 Hz, C9H), 6.33 (1H, m, C4H), 6.22 (1H, m, C22H), 6.15 (1H, d, J=0.01 Hz, C21H), 6.12 (1H, t, J=0.02 Hz, C3H), 4.35 (2H, D, J=0.02 Hz, C19H), 3.80 (3H, s, C17H), 3.78 (3H, s, C11H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.41 (C12), 166.52 (C6), 161.26 (C16), 160.56 (C10), 142.64 (C23), 139.15 (C20), 137.27 (C13), 135.35 (C2), 134.82 (C4), 131.07 (C15), 130.17 (C9), 126.14 (C7), 125.19 (C1), 120.09 (C5), 117.74 (C3), 113.60 (C14), 113.02 (C8), 110.51 (C22), 107.96 (C21), 55.40 (C17 and C11), 42.84 (C19).


HRMS: Calcd. for M+. (C26H23NO4) m/z=413.16271. found 413.1614 (3 ppm)


Anal. Cald for: C, 75.53; H, 5.61; N, 3.39, O, 15.48. found C, 74.96; H, 5.59; N, 3.36.


Ligand O: 1-(4-methoxybenzoyl)-6-(1-(pyridine-2-methyl)amino)-6-(4-methoxyphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.38 (1H, s, N18H), 8.53 (1H, d, J=0.01 Hz, C24H), 7.80 (2H, d, J=0.03 Hz, C14H), 7.70 (1H, t, J=0.02 Hz, C22H), 7.42 (1H, d, J=0.02 Hz, C21H), 7.33 (2H, d, J=0.02 Hz, C8H), 7.22-7.17 (2H, m, C2H and C23H), 6.96 (4H, d, J=0.03 Hz, C15H and C9H), 6.47 (1H, m, C4H), 6.26 (1H, t, J=0.02 Hz, C3H), 4.67 (2H, d, J=0.03 Hz, C19H), 3.88 (3H, s, C17H), 3.87 (3H, s, C11H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.46 (C12), 166.80 (C6), 161.35 (C16), 160.55 (C10), 156.90 (C24), 149.01 (C22), 139.34 (C20), 137.61 (C13), 135.57 (C2), 134.68 (C4), 131.14 (C15), 130.01 (C9), 125.90 (C7), 125.44 (C1), 122.65 (C21), 121.45 (C23), 120.19 (C5), 117.92 (C3), 113.67 (C14), 113.08 (C8), 55.39 (C17 and C11), 50.99 (C19).


HRMS: Calcd. for M+. (C27H24N2O3) m/z=424.17869. found 424.1775 (2 ppm).


Anal. Cald for C27H24N2O3: C, 76.39; H, 5.70; N, 6.60, O, 11.31. found C, 76.20; H, 5.73; N, 6.77.


Ligand P: 1-(3,4,5-trimethoxybenzoyl)-6-(benzylamino)-6-(3,4,5-trimethoxyphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.36 (1H, t, J=0.02 Hz, N20H), 7.33-7.22 (6H, m, C2H, C23H, C24H and C25H), 7.03 (2H, s, C15H), 6.57 (1H, m, C4H), 6.51 (2H, s, C8H), 6.27 (1H, t, J=0.01 Hz, C3H), 4.50 (2H, d, J=0.02 Hz, C21H), 3.92 (12H, s, C11H and C18H), 3.74 (6H, s, C12H and C19H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.40 (C13), 166.52 (C6), 152.95 (C16), 152.60 (C9), 139.70 (C17), 139.39 (C10), 138.70 (C14), 137.58 (C22), 137.53 (C2), 135.64 (C4), 128.96 (C7), 128.80 (C24), 127.64 (C23), 124.78 (C1), 119.46 (C5), 118.17 (C3), 106.42 (C15), 105.63 (C8), 61.05 (C19), 60.94 (C12), 56.26 (C18), 56.12 (C11), 49.56 (C21).


HRMS: Calcd. for M+. (C32H33NO7) m/z=543.22570. found 543.2273 (2 ppm).


Anal. Cald for C32H33NO7: C, 70.70; H, 6.12; N, 2.58, O, 20.60. found C, 70.93; H, 6.21; N, 2.61.


Ligand Q: 1-(3,4,5-trimethoxybenzoyl)-6-(1-(furan-2-methyl)amino)-6-(3,4,5-trimethoxy phenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.13 (1H, t, J=0.02 Hz, N20H), 7.38 (1H, m, C25H), 7.21 (1H, q, J=0.01 Hz, C2H), 7.00 (1H, s, C15H), 6.69 (1H, s, C8H), 6.58 (1H, q, J=0.01 Hz, C4H), 6.34 (1H, q, J=0.01 Hz, C24H), 6.29-6.25 (2H, m, C3H and C23H), 4.47 (2H, d, J=0.02 Hz, C21H), 3.96 (3H, s, C19H), 3.92 (3H, s, C12H), 3.91 (6H, s. C18H), 3.87 (6H, s, C11H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.37 (C13), 166.03 (C6), 153.08 (C16), 152.57 (C9), 149.95 (C25), 142.65 (C22), 139.70 (C17), 139.63 (C10), 138.82 (C14), 137.44 (C2), 135.86 (C4), 128.82 (C7), 124.92 (C1), 119.39 (C5), 118.31 (C3), 110.61 (C22), 108.12 (C15), 105.85 (C8), 61.06 (C19), 60.93 (C12), 56.27 (C18), 56.25 (C11), 42.92 (C21).


HRMS: Calcd. for M+. (C30H31NO8) m/z=533.20497. found 533.2035 (2 ppm).


Anal. Cald for C30H31NO8: C, 67.53; H, 5.86; N, 2.63, O, 23.99. found C, 67.82. H, 5.99; N, 4.94.


Ligand R: 1-(3,4,5-trimethoxybenzoyl)-6-(1-(Pyridine-2-methyl)amino)-6-(3,4,5-trimethoxyphenyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 14.30 (1H, t, J=0.02 Hz, N20H−, 8.55 (1H, d, J=0.01 Hz, C26H), 7.70 (1H, t, J=0.02 Hz, C24H), 7.38 (1H, d, J=0.03 Hz, C23H), 7.24-7.18 (2H, m, C2H and C25H), 7.02 (1H, s, C15H), 6.62 (1H, s, C8H), 6.58 (1H, q, J=0.02 Hz, C4H), 6.27 (1H, t, J=0.01 Hz, C3H), 4.65 (2H, d, J=0.02 Hz, C21H), 3.92 (12H, s, C11H and C18H), 3.75 (6H, s, C12H and C19H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 190.38 (C13), 166.68 (C6), 157.03 (C26), 152.98 (C16), 152.56 (C9), 149.60 (C25), 139.62 (C17 and C10), 138.82 (C14), 137.46 (C2), 137.01 (C22), 135.94 (C4), 128.89 (C7), 124.96 (C1), 122.58 (C25), 121.36 (C23), 119.50 (C5), 118.31 (C3), 106.48 (C15), 105.80 (C8), 61.01 (C19), 60.93 (C12), 56.24 (C18), 56.15 (C11), 51.27 (C21).


HRMS: Calcd. for M+. (C31H32N2O7) m/z=544.22095. found 544.2181 (5 ppm).


Anal. Cald for C31H32N2O7: C, 68.37; H, 5.92; N, 5.14, O, 20.56. found C, 68.16; H, 6.02; N, 4.96.


Ligand S: 1-furanoyl-6-benzylamino-6-furanyl fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 13.90 (1H, s, N16H), 7.80 (1H, q, J=0.01 Hz, C15H), 7.68-7.67 (2H, m, C10H and C13H), 7.35-7.21 (5H, m, C19H, C20H and C21H). 7.20 (1H, m, C2H), 6.92 (1H, q, J=0.01 Hz, C14H), 6.76 (1H, d, J=0.01 Hz, C8H), 6.59-6.57 (2H, m, C4H and C9H), 6.39 (1H, t, J=0.01 Hz, C3H), 4.65 (2H, d, J=0.02 Hz, C17H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 176.37 (C11), 154.33 (C7), 153.95 (C12), 146.13 (C6), 145.32 (C15), 144.65 (C10), 137.64 (C2), 137.07 (C18), 134.91 (C4), 128.73 (C20), 127.69 (C21), 127.44 (C19), 124.71 (C1), 119.88 (C5), 118.83 (C3), 117.55 (C13), 117.34 (C14), 11.60 (C8), 111.45 (C9), 50.03 (C17).


HRMS: Calcd. for M+. (C22H17NO3) m/z=343.12084. found 343.1210 (0 ppm).


Anal. Cald for C22H17NO3: C, 76.95; H, 4.99; N, 4.08, O, 13.98. found C, 76.75; H, 5.15; N, 3.95.


Ligand T: 1-(furanoyl)-6-(1-(furan-2-methyl)amino)-6-(furanyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 13.76 (1H, s, N16H), 7.79 (1H, q, J=0.01 Hz, C15H), 7.70 (1H, m, C10H), 7.66 (1H, m, C13H), 7.36 (1H, m, C19H), 7.19 (1H, d, J=0.01 Hz, C2H), 6.91 (1H, q, J=0.01 Hz, C14H), 6.84 (1H, d, J=0.01 Hz, C21H), 6.62 (1H, q, J=0.01 Hz, C20H), 6.56 (1H, q, J=0.01 Hz, C4H), 6.38 (1H, t, J=0.01 Hz, C3H), 6.31 (1H, m, C8H), 6.27 (1H, m, C9H), 4.62 (2H, d, J=0.02 Hz, C17H)



13C NMR (CDCl3, 50 MHz, ppm) δ: 176.36 (C11), 153.93 (C7), 153.85 (C12), 149.92 (C21), 146.01 (C6), 145.32 (C15), 144.80 (C10), 142.61 (C18), 137.94 (C2), 134.98 (C4), 124.84 (C1), 119.83 (C5), 119.82 (C3), 117.59 (C13 and C14), 111.60 (C8), 111.52 (C9), 110.52 (C20), 108.02 (C19), 43.07 (C17).


HRMS: Calcd. for M+. (C20H15NO4) m/z=333.10011. found 333.1008 (2 ppm).


Anal. Cald for C20H15NO4: C, 72.06; H, 4.54; N, 4.20, O, 19.20. found C, 72.11; H, 4.55; N, 4.18.


Ligand U: 1-(furanoyl)-6-(1-(pyridine-2-methyl)amino)-6-(furanyl) fulvene



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1H NMR (CDCl3, 300 MHz, ppm) δ: 13.90 (1H, s, N16H), 8.54 (1H, d, J=0.02 Hz. C22H), 7.80 (1H, q, J=0.01 Hz, C15H), 7.70-7.60 (3H, m, C10H, C13H and C24H), 7.42 (1H, d, J=0.03 Hz, C19H), 7.21-7.17 (2H, m, C21H and C2H), 6.92 (1H, q, J=0.01 Hz, C14H), 6.79 (1H, d, J=0.01 Hz, C8H), 6.57-6.54 (2H, m, C4H and C9H), 6.38 (1H, t, J=0.01 Hz, C3H), 4.78 (2H, d, J=0.02 Hz, C17H).



13C NMR (CDCl3, 50 MHz, ppm) δ: 176.40 (C11), 157.15 (C22), 154.59 (C7), 153.92 (C12), 149.35 (C20), 145.94 (C6), 145.35 (C15), 144.92 (C10), 137.98 (C2), 137.01 (C18), 135.15 (C4), 124.88 (C1), 122.45 (C19), 121.25 (C21), 119.87 (C5), 119.07 (C3), 117.63 (C13) 117.59 (C14), 111.61 (C8), 111.37 (C9), 51.77 (C17).


HRMS: Calcd. for M+. (C21H16N2O3) m/z=344.11609. found 344.1155 (1 ppm).


Anal. Cald for C21H16N2O3: C, 73.24; H, 4.68; N, 8.13, O, 13.94. found C, 72.77; H, 4.73; N, 7.76.


Preparation of Metallic Complexes from Carbonylaminofulvenes


CrCl3/Ligand A Complex.


7.51 mg (20 μmol) of ligand A and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl2/Ligand A Complex.


7.51 mg (20 μmol) of ligand A and 1.23 (10 μmol) of CrCl2 were introduced in a Schlenk with 100 μL of THF. The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand D Complex.


7.27 mg (20 μmol) of ligand D and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand H Complex.


9.31 mg (20 μmol) of ligand H and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand E Complex.


7.07 mg (20 μmol) of ligand E and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a red brown solid.


CrCl3/Ligand C Complex.


7.53 mg (20 μmol) of ligand C and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand B Complex.


7.31 mg (20 μmol) of ligand B and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand O Complex.


8.49 mg (20 μmol) of ligand O and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl3/Ligand L Complex.


10.89 mg (20 μmol) of ligand L and 3.75 mg (10 μmol) of CrCl3.3THF were introduced in a Schlenk with 100 μL of tetrahydrofuran (THF). The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.


CrCl2/Ligand L Complex.


10.89 mg (20 μmol) of ligand L and 1.23 (10 μmol) of CrCl2 were introduced in a Schlenk with 100 μL of THF. The mixture was placed under stirring for 2 h at room temperature. The solvent was evaporated under vacuum overnight to yield a yellow brown solid.




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The complex was recrystallised by slow diffusion of pentane in a saturated solution of the complex in THF. The crytals obtained were suitable for X-Ray analysis. The complex crystallises in a monoclinic environment with space group P 21/c. The chromium atom is coordinated by one molecule of tridentate fulvene by its oxygen atom and its two nitrogen atoms. The chromium atom is further coordinated by two chlorine atom and a THF molecule. This can be seen in FIG. 3. The complex is characterised as follows.















Empirical formula
C43 H39 Cl2 Cr N2 O2


Formula weight
738.66


Temperature
100(2) K


Wavelength
0.71073 A


Crystal system, space group
Monoclinic, P 21/c


Unit cell dimensions
a = 14.987(2) A alpha = 90 deg.



b = 14.175(2) A beta = 99.485(9) deg.



c = 17.412(3) A gamma = 90 deg.


Volume
3648.4(9) A{circumflex over ( )}3


Z, Calculated density
4, 1.345 Mg/m{circumflex over ( )}3


Absorption coefficient
0.500 mm{circumflex over ( )}−1


F(000)
1540


Crystal size
0.2 × 0.2 × 0.03 mm


Theta range for data collection
2.92 to 27.48 deg.


Limiting indices
−19 <= h <= 19, −18 <= k <=



11, −22 <= l <= 22


Reflections collected/unique
38703/8296 [R(int) = 0.0659]


Completeness to theta =
27.48 99.2%


Absorption correction
Semi-empirical from equivalents


Max. and min. transmission
0.985 and 0.885


Refinement method
Full-matrix least-squares on F{circumflex over ( )}2


Data/restraints/parameters
8296/0/451


Goodness-of-fit on F{circumflex over ( )}2
1.030


Final R indices [I >
R1 = 0.0423, wR2 = 0.0840


2sigma(I)]



R indices (all data)
R1 = 0.0728, wR2 = 0.0941


Largest diff. peak and hole
0.331 and −0.492 e.A{circumflex over ( )}−3










Homogeneous polymerisation of ethylene.


The metallic catalyst component were activated with 1.625 mL of methylaluminoxane (MAO). The solution was stirred for 5 minutes and then diluted with 3.375 mL of toluene. The reactor was dried under nitrogen at a temperature of 90° C. for a period of time of 30 minutes. The reactor was brought to a polymerisation temperature of 35° C. and 50 mL of toluene were added to the reactor under nitrogen. A scavenger solution consisting of 0.5 mL of MAO (30%) and 4.5 mL of toluene was added to the reactor and the solution was stirred for a few minutes. The solution of activated catalyst was added to the reactor under nitrogen. The flux of nitrogen was interrupted, the reactor was purged and placed under an ethylene pressure of 15 bars. It was placed under stirring for a period of time of 1 h. The reactor was purged and the polymerisation was stopped by adding a 10% solution of MeOH/HCl. The polymer was washed 3 times with 30 mL of MeOH and 3 times with 30 mL of acetone. The polymer was dried under vacuum overnight at room temperature. The results are summarised in Table IV for the chromium-based catalyst systems.













TABLE IV







Activity

Tm


M/L
m PE (g)
(kgPE/(mol · h)
Mn
(° C.)



















CrCl3/A
0.941
94.1

137


CrCl2/A
0.976
97.6
insoluble
137


CrCl3/D
0.995
99.5
unfilterable
119


CrCl3/H
1.045
104.5
unfilterable
135


CrCl3/E
1.244
124.4
insoluble
129


CrCl3/C
1.283
128.3
unfilterable
135


CrCl3/B
2.895
289.5
unfilterable
133


CrCl3/O
3.648
364.8
insoluble
136


CrCl3/L
5.415
541.5
insoluble
135


CrCl2/L
6.915
691.5
insoluble
136









For all polymerisations, the conditions were as follows: Cr 10 μmol, ligand 20 μmol, polymerisation temperature 35° C., ethylene pressure 15 bars, 1000 eq. MAO, solvent: toluene, polymerisation time 1 h.


The highest activities were obtained with the catalyst systems based on CrCl3/ligand L and CrCl2/ligand L. As depicted in Table V, CrCl2 based system is a selective catalyst whereas CrCl3 based system is a mixed polymer/oligomer catalyst.













TABLE V








Activity
Consumption



M/L
m PE (g)
(kgPE/(mol · h)
(kgC2H4/(mol · h))








CrCl2/L
4.11
411
385



CrCl3/L
3.38
338
590









For all polymerisations, the conditions were as follows: Cr 10 μmol, ligand 20 μmol, polymerisation temperature 35° C., ethylene pressure 15 bars, 1000 eq. MAO, solvent: toluene, polymerisation time 1 h.


The activity of the system CrCl2/ligand L has been studied as a function of temperature and of ethylene pressure. The results are displayed in Table VI. It can be concluded that the activity of the catalyst system increases with increasing pressure and decreases when the temperature is raised above 35° C. It can also be concluded that the activity increases with a lower amount of catalyst.











TABLE VI








5 μmol Cr
2.5/μmol Cr











(kgPE/(mol · h)
15 bars

45 bars
45 bars





25° C.
773

1 722
3 606


35° C.
1 016  

custom character

1 341
2 790


55° C.
619

  806
1 196









For all polymerisations, the conditions were as follows: 1000 eq. MAO, solvent: toluene, polymerisation time 1 h.


The consumptions were also measured and the results are displayed in Table VII.













TABLE VII






Temp.
m PE
Activity
Consumption



(° C.)
(g)
(kgPE/(mol · h)
(kgC2H4/(mol · h)




















35
7.49
2 996
2 729



25
10.77
4 308
5 738









For all polymerisations, the conditions were as follows: Cr 2.5 μmol, ligand L 5 μmol, ethylene pressure 45 bars, 1000 eq. MAO, solvent: toluene, polymerisation time 1 h.


Polymerisation of Ethylene with Supported Catalyst Systems.


The activity of the unsupported CrCl2/ligand L catalyst system was evaluated in heptane. The catalyst system was not selective in polyethylene as the consumption of ethylene was larger than the amount of ethylene present in the polyethylene. The polymerisation conditions were as follows:

  • complexation time: 2 hours,
  • 5 μmol of ligand with 2.5 μmol of Cr,
  • polymerisation temperature: 25° C.,
  • polymerisation pressure: 45 bars,
  • 1000 equ. of MAO,
  • solvent: heptane,
  • polymerisation time: 1 hour.


The results are displayed in Table VIII.













TABLE VIII







Activity
Consumption
Tm



m PE (g)
(kgPE/(mol · h)
(kgC2H4/(mol · h)
(° C.)








6.77
2 708
6 768
137










Impregnation of the Catalyst on Silica/MAO.


5 μmol of complex CrCl2/L were dissolved in 600 μl of toluene and then introduced in a schlenk with 100 mg of silica/MAO (50 μmolCr/gSi) under stirring for a period of time of 30 minutes. The impregnated silica was filtered and washed either once with 600 μl of toluene and three times with 600 μl of heptane (condition 1) or three times with 600 μl of heptane (condition 2).


Polymerisation of Ethylene with Impregnated Silica/MAO.


The reactor was dried under nitrogen for a period of time of 30 minutes and at a temperature of 90° C. 50 mL of heptane were then introduced into the reactor with 100 mL of scavenger, MAO (30%) diluted in 5 mL of heptane, at a temperature of 25° C. 50 mg of silica, containing about 2.5 μmol of activated catalyst (50 μmolCr/gSiO2) were introduced into the reactor with 5 mL of heptane. The polymerisation reaction was carried out at a temperature of 25° C. under an ethylene pressure of 45 bars and for a period of time of 1 hour for conditions 1 and 2. The results are displayed in Table IX.
















TABLE IX







m PE
Activity
Consumption
Activity
Consumption
Tm



(g)
(kgPE/mol · h)
(kgC2H4/(mol · h)
(gPE/(gsi · h))
(gC2H4/(gsi · h))
(° C.)






















Cond. 1
~0
0
4 836
0
242



Cond. 2
0.77
308
5 061
15.4
253
138










Polymerisation of alpha-olefins.


The unsupported catalyst system CrCl2/L was used for the polymerisaton of hexene with the following conditions: CrCl2/L/MAO/hexene=1/100/2000. After a period of time of 24 hours and a polymerisation temperature of 30° C. the yield was of about 4.5%.

Claims
  • 1. A method for preparing a metallic complex comprising: preparing a carbonylamino fulvene ligand by condensation reaction of an hydroxycarbonyl fulvene ligand with a primary amine;
  • 2. The method of claim 1, wherein R1 is an alkyl, a substituted or an unsubstituted phenyl group, or CHPh2, wherein phenyl group Ph is substituted or unsubstituted, or a heteroatom-containing group.
  • 3. The method of claim 2, wherein R1 is CHPh2, paramethoxyphenyl or cyclohexyl.
  • 4. The method of claim 1, wherein R2 is CH2pyridine or CH2furan.
  • 5. The method of claim 1, wherein R1 is CHPh2 and R2 is CH2pyridine, or wherein R1 is paramethoxyphenyl and R2 is CH2pyridine, or wherein R1 is cyclohexyl and R2 is CH2furan.
  • 6. The method of claim 1, wherein M is Cr(II), Cr(III) or Ni.
  • 7. The method of claim 1, wherein Z is halogen or acetate.
  • 8. A metallic complex obtained by the method of claim 1.
  • 9. An active catalyst comprising the metallic complex of claim 8, an activating agent having an ionising action and optionally a support.
  • 10. The active catalyst system of claim 9, wherein the activating agent is methylaluminoxane.
  • 11. A method for preparing an active catalyst system comprising: providing a carbonylamino fulvene ligand;complexing the ligand with a metallic salt MZn in a solvent, wherein M is a metal Group 6 to 11 of the Periodic Table, Z is a negative counter-anion and n is the valence of M;retrieving a catalyst component;optionally depositing the catalyst component on a support;activating the catalyst component with an activating agent having an ionising action;optionally adding a scavenger; andretrieving an active oligomerisation or polymerisation catalyst system.
  • 12. A method for oligomerising or for homo- or co-polymerising ethylene and alpha-olefins comprising: injecting the active catalyst system of claim 9 into a reactor;injecting the monomer and optional comonomer into the reactor;maintaining the reactor under polymerisation conditions; andretrieving oligomers and/or polymer.
  • 13. The method of claim 12, wherein the monomer and comonomer are selected from ethylene, propylene or 1-hexene.
Priority Claims (1)
Number Date Country Kind
07290931 Jul 2007 EP regional
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2008/059282 7/16/2008 WO 00 8/23/2010
Publishing Document Publishing Date Country Kind
WO2009/013196 1/29/2009 WO A
Foreign Referenced Citations (1)
Number Date Country
1 997 834 Dec 2008 EP
Non-Patent Literature Citations (1)
Entry
Duda, L.; Erker, G.; Frohlich, R.; Zippel, F., Eur. J. Inorg. Chem., 1998, 1153-1162.
Related Publications (1)
Number Date Country
20100311931 A1 Dec 2010 US