CN103275111B - To mix the early transition metal title complex of phenyl, synthetic method and application based on amidino groups boron - Google Patents
To mix the early transition metal title complex of phenyl, synthetic method and application based on amidino groups boron Download PDFInfo
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Abstract
The present invention relates to a class to mix the early transition metal title complex of phenyl, synthetic method and purposes based on amidino groups boron, this type of title complex is reacted by mix phenyl ligands and early transition metal halogenide (halogen refers to fluorine, chlorine, bromine, iodine) of amidino groups boron or is reacted obtained respectively with metal alkyl compound again.Such title complex in the presence of an activator, or activator and promotor jointly in the presence of can catalyzed ethylene homopolymerization, simultaneously also can the copolymerization of catalyzed ethylene and 1-hervene copolymer and ethene and alhpa olefin.The structural formula general formula of this type of title complex is as follows.
Description
Technical field
The present invention relates to a class to mix the early transition metal title complex of phenyl, synthetic method and for olefin polymerization catalysis based on amidino groups boron.Such title complex promotor or activator and promotor jointly in the presence of the catalyst system that formed can catalysis in olefine polymerization.
Technical background
After nineteen fifties has found Ziegler-Natta catalyst, multiple heterogeneous catalysis system has been developed, wherein MgCl
2the titanium catalyst of load shows highly active catalytic performance, (K.Ziegler, etc., Angew.Chem.1995,67,424; K.Ziegler, etc., Angew.Chem.1995,67,541.), but the heterogeneous catalysis system of this dynamics model, be difficult to the Structure and Properties by regulating catalyst structure to control polymkeric substance.The 4th subgroup cyclopentadienyl catalyst developed subsequently then solves this kind of problem well, and " CGC " type half metallocene wherein with constrained geometry has become one of industrial most important single active catalyst (J.C.Stevens, F.J.Timmers; J.C.Wilson, Stevens, F.J.Timmers; D.R.Wilson; G.F.Schmidt, P.N.Nickias, R.K.Rosen; G.W.Knight; S.-Y.Lai, (Dow) Eur.Pat.Appl.EP0416815,1991; Chem.Abstr.1991,115,93163; B) J.A.M.Canich, (Exxon) Eur.Pat.Appl.EP0420436,1991; Chem.Abstr.1991,115,184145.).
Nineteen ninety, J.E.Bercaw group has designed and synthesized the tetramethyl-ring pentadienyl dianion part [C of the nitrogen anion side chain containing silyl-bridged
5me
4siMe
2n
tbu]
2-, and synthesized " CGC " type transition metal complex [C based on this part first
5me
4siMe
2n
tbu] ScX, wherein X is CH (SiMe
3)
2or H.Research finds that this hydride can as oligomerisation (Shapiro, the P.J. of single component catalyst catalyzing propone, 1-butylene and 1-amylene; Bunel, E.; Schaefer, W.P.; Bercaw, J.E.Organometallics1990,9,867.).
J.Okuda group, on the basis of this work, adopts the strategy that alkane is eliminated, first by rare earth metal trialkyl title complex [Y (CH
2siMe
3)
3(THF)
2] and [C
5me
4h] SiMe
2nHCMe
2x (X=Me, Et) react, synthesized as shown in the formula " CGC " type rare earth metal yttrium monoalkyl title complex.These alkyl complexes can with the polymerization of medium activity catalyzed ethylene, alpha-olefin and polar monomer.Under hydrogen effect, these alkyl complexes can be further converted to hydride, accordingly without tetrahydrofuran (THF) coordination hydride can catalyzed ethylene, tert. butylacrylate, vinyl cyanide polymerization (a.Hultzsch, K.C.; Spaniol, T.P.; Okuda, J.Angew.Chem.Int.Ed.1999,38,227; B.Hultzsch, K.C.; Voth, P.; Beckerle, K.; Spaniol, T.P.; Okuda, J.Organometallics2000,19,228.).
Little " CGC " type rare earth metal allyl complex be combined into of Cui winter plum is shown below, and by studying their catalytic activity, finds that the type title complex of rare earth metal gadolinium is at Al
ibu
3[PhMe
2nH] [B (C
6f
5)
4] under acting in conjunction, can Isosorbide-5-Nitrae-cis polymerization of catalysis isoprene, obtain polyisoprene (Jian, Z. highly-solid selectively; Cui, D.; Hou, Z.; Li, X.Chem.Commun.2010,46,3022.).
Summary of the invention
The object of the invention is to provide the early transition metal title complex of a class based on amidino groups borabenzene ligands, is the catalyzer of a class for olefinic polymerization.
The present invention also provides the synthetic method of above-mentioned title complex.
Another object of the present invention is to provide the purposes of above-mentioned title complex.Namely under promotor exists, or activator and promotor jointly in the presence of for catalysis in olefine polymerization, alkene comprises ethene, alpha-olefin etc., comprises and is gathered in interior homopolymerization and copolymerization.
The structural formula of the early transition metal title complex based on amidino groups borabenzene ligands provided by the invention is as follows:
In structure above:
M is rare earth ion or other early transition metal ion, and described rare earth ion is Sc, Y or lanthanide ion, is preferably Sc, Y or Lu ion; Described early transition metal ion is the 4th or the 6th group 4 transition metal ion, is preferably Zr or Cr ion;
R
1, R
3and R
5for H; R
2and R
4for the alkyl of H or C1 ~ C4; R
6or R
8for C1-C8 alkyl; R
7for the alkyl or phenyl of C1-C4;
X: be halogen, the alkyl of C1 ~ C4 or C1 ~ C4 alkyl of silicon (C1 ~ C6) alkyl replacement; Halogen refers to fluorine, chlorine, bromine or iodine; Preferred halogen is chlorine;
for coordinate bond;
N is 2 or 3.
Preferably based on the following structural formula of early transition metal title complex of amidino groups borabenzene ligands:
A class provided by the invention is based on the early transition metal title complex of amidino groups borabenzene ligands, and its synthetic method is as follows:
A, in organic solvent and at-70 ~ 50 DEG C, react 5 ~ 60min by amidino groups borabenzene ligands an alkali metal salt and rare-earth metal chloride or other early transition metal muriate with mol ratio 1:0.1 ~ 6, obtaining X is that the amidino groups boron of halogen is mixed benzene early transition metal title complex.Basic metal is Li or K.Other early transition metal is the 4th or the 6th group 4 transition metal.
B, in organic solvent and at-70 ~ 50 DEG C, be that the amidino groups boron of halogen benzene early transition metal title complex of mixing reacts 5 ~ 60min with lithium reagent with mol ratio 1:0.1 ~ 6 again and synthesizes by obtaining X in a, obtaining X is that the amidino groups boron of alkyl is mixed benzene early transition metal title complex.Lithium reagent is the hydrocarbyl lithium of C1 ~ C4 or C1 ~ C8 lithium alkylide of silicon (C1 ~ C6) alkyl replacement.
Described amidino groups borabenzene ligands has following structural formula:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8as previously mentioned.
Described organic solvent prioritizing selection tetrahydrofuran (THF) or toluene.
Described early transition metal preferentially elects Sc, Y, Lu, Zr or Cr as; Described X prioritizing selection chlorine.
The present invention's synthesis mix the early transition metal title complex of phenyl under promotor exists based on amidino groups boron, or activator and promotor jointly in the presence of for catalysis in olefine polymerization, described olefinic polymerization refers to homopolymerization or copolymerization, and described alkene refers to ethene or C
3-C
6alpha-olefin.Described activator refers to [Ph
3c] [B (C
6f
5)
4], [PhNMe
2h] [B (C
6f
5)
4], B (C
6f
5)
3boride; Described promotor is methylaluminoxane, isobutyl aluminium alkoxide, the methylaluminoxane of modification or AlR
3, R be Me, Et,
ibu,
ibu
2h or CH
2siMe
3.
Be aggregated in organic solvent toluene, carry out under-20 ~ 100 DEG C of conditions.
The early transition metal title complex of phenyl of mixing based on amidino groups boron of the present invention, can obtain extraordinary effect for olefin catalytic polymerization, be applicable to industrialized generation.
Accompanying drawing explanation
The single crystal structure figure of Fig. 1 amidino groups borabenzene ligands lithium salts LiL1;
Fig. 2 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C1;
Fig. 3 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C2;
Fig. 4 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C3;
Fig. 5 amidino groups boron is mixed the single crystal structure figure of benzene zirconium complex C4;
Fig. 6 amidino groups boron is mixed the single crystal structure figure of benzene chromic compound C5;
Fig. 7 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C6;
Fig. 8 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C7;
Fig. 9 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C8;
Figure 10 amidino groups boron is mixed the single crystal structure figure of benzene chromic compound C9;
Figure 11 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C11;
Figure 12 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C13;
Figure 13 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C14;
Figure 14 amidino groups boron is mixed the single crystal structure figure of benzene rare earth compounding C15;
Embodiment
To contribute to understanding the present invention further by following embodiment, but content of the present invention can not be limited.
Embodiment 1
Mix trimethylammonium phosphorus boron benzene (512mg, 3.37mmol) and N, N '-di-isopropyl-2-methyl amidino lithium salts (499mg, 3.37mmol) be mixed in the mixing solutions of 2mL toluene and 1mL tetrahydrofuran (THF), under 110 DEG C of conditions, reacting by heating 6 days, obtains yellow suspension, by this suspension liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane, then vacuum-drying obtains light yellow solid LiL1740mg, productive rate 98%.
1hNMR (400MHz, THF-d
8, 25 DEG C): δ (ppm) 7.21 (dd,
3j
hH=10.0Hz,
3j
hH=7.2Hz, 2H, 3-/5-H), 6.09 (dt,
3j
hH=7.2Hz,
4j
hH=0.8Hz, 1H, 4-H), 6.02 (dd,
3j
hH=9.6Hz,
4j
hH=0.8Hz, 2H, 2-/6-H), 3.98 (sept,
3j
hH=6.6Hz, 1H, CHMe
2), 3.52 (sept,
3j
hH=6.4Hz, 1H, CHMe
2), 2.04 (s, 3H, NC (Me) N), 1.09 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.91 (d,
3j
hH=6.4Hz, 6H, CHMe
2).
13cNMR (100MHz, THF-d
8, 25 DEG C): δ (ppm) 164.5 (NC (Me) N), 135.5,123.5 (br), 112.1 (boratabenzene-C), 49.2,47.5 (CHMe
2), 25.1,24.5,12.8 (NC (Me) NandCHMe
2).
11bNMR (128MHz, THF-d
8, 25 DEG C): δ (ppm) 37.0.C
13h
22bLiN
2elemental analysis data: calculated value: C, 69.68; H, 9.90; N, 12.50. measured value: C, 68.92; H, 9.59; N, 12.32.
Embodiment 2
At-30 DEG C, the toluene solution (141mg, 1.00mmol) of 2mL boron chlorine is added drop-wise to N, in toluene (6mL) suspension liquid of N '-di-isopropyl-2-methyl amidino lithium salts (150mg, 1.00mmol).After dropwising ,-30 DEG C are reacted 1 hour, then centrifugal, transfer supernatant liquor.By clear liquid under vacuo except desolventizing, obtain yellow jelly 217mg, be dissolved in 6mL tetrahydrofuran (THF), at-30 DEG C, then add the tetrahydrofuran solution (2mL) of the silica-based ammonium potassium (176mg, 0.88mmol) of hexamethyl two to it.After dropwising ,-30 DEG C are reacted 1 hour, and then reaction solution is risen to room temperature naturally, stirring reaction spends the night.Reaction solution is under vacuo except desolventizing, and with the extraction of 3 × 5mL toluene, yellow extraction liquid is concentrated into 1.5mL, then leaves standstill at-30 DEG C, and separate out yellow solid, this solid 1mL n-hexane, then vacuum-drying obtains light yellow solid KL2133mg, productive rate 47%.(note: about 80% purity is difficult to purifying, does not affect subsequent reactions.）
1HNMR(400MHz,THF-d
8,25℃):δ(ppm)5.67(s,1H,4-H),5.64(s,1H,2-/6-H),4.37(sept,
3J
H-H=6.8Hz,1H,CHMe
2),3.49(sept,
3J
H-H=7.2Hz,1H,CHMe
2),2.13(s,6H,3-/5-Me),1.91(s,3H,NC(Me)N),1.14(d,
3J
H-H=6.4Hz,6H,CHMe
2),0.93(d,
3J
H-H=6.0Hz,6H,CHMe
2).
11BNMR(128MHz,THF-d
8,25℃):δ(ppm)34.7.
Embodiment 3
At-30 DEG C, the toluene solution (141mg, 1.00mmol) of 2mL boron chlorine is added drop-wise to N, in toluene (6mL) suspension liquid of N '-dicyclohexyl-2-methyl amidino lithium salts (373mg, 1.00mmol).After dropwising ,-30 DEG C are reacted 1 hour, then centrifugal, transfer supernatant liquor.By this clear liquid under vacuo except desolventizing, obtain yellow jelly 287mg, be dissolved in 6mL tetrahydrofuran (THF), at-30 DEG C, then add the tetrahydrofuran solution (2mL) of the silica-based ammonium potassium (198mg, 0.88mmol) of hexamethyl two to it.After dropwising, react at-30 DEG C, along with the carrying out of reaction, adularescent Precipitation.After 1 hour, reaction solution is risen to room temperature naturally, stirring reaction spends the night, centrifugal, and removing supernatant liquor, lower floor's white precipitate 3 × 3mL n-hexane, then vacuum-drying obtains white solid KL3218mg, productive rate 60%.
1HNMR(400MHz,THF-d
8,25℃):δ(ppm)5.65(s,1H,4-H),5.60(s,2H,2-/6-H),3.75(m,1H,N(CH
2)CH(CH
2)),3.58(m,1H,N(CH
2)CH(CH
2)),2.11(s,6H,3-/5-Me),1.69～0.88(m,20H,(CH
2)
5),1.91(s,3H,NC(Me)N).
Embodiment 4
At-30 DEG C, the toluene solution (141mg, 1.00mmol) of 2mL boron chlorine is added drop-wise to N, in toluene (6mL) suspension liquid of N '-di-isopropyl-2-phenyl amidino groups lithium salts (211mg, 1.00mmol).After dropwising ,-30 DEG C are reacted 1 hour, then centrifugal, transfer supernatant liquor.By this clear liquid under vacuo except desolventizing, obtain yellow jelly 280mg, be dissolved in 6mL tetrahydrofuran (THF), at-30 DEG C, then add the tetrahydrofuran solution (2mL) of the silica-based ammonium potassium (182mg, 0.91mmol) of hexamethyl two to it.After dropwising ,-30 DEG C are reacted 1 hour, and then reaction solution is risen to room temperature naturally, stirring reaction spends the night.Reaction solution except desolventizing, obtains red foam shape solid under vacuo.Used 3 × 3mL n-hexane, then vacuum-drying obtains red solid KL4176mg, productive rate 81%.
1HNMR(400MHz,THF-d
8,25℃):δ(ppm)7.35(t,
3J
HH=8.0Hz,2H,Ph-H),7.25(t,
3J
HH=7.2Hz,1H,Ph-H),7.19(d,
3J
HH=8.0Hz,2H,Ph-H),5.78(s,2H,2-/6-H),5.74(s,1H,4-H),3.43(sept,
3J
HH=6.8Hz,1H,CHMe
2),2.88(sept,
3J
HH=5.6Hz,1H,CHMe
2),2.16(s,6H,3-/5-Me),1.01(d,
3J
HH=6.4Hz,6H,CHMe
2),0.72(d,
3J
HH=6.4Hz,6H,CHMe
2).
13CNMR(100MHz,THF-d
8,25℃):δ(ppm)165.8(NC(Me)N),141.8,140.3,128.5,128.1,127.2,123.47,111.1(boratabenzene-CandPh-C),49.6,47.9(CHMe
2),25.8,25.7,24.3(3-/5-MeandCHMe
2).
11BNMR(128MHz,THF-d
8,25℃):δ(ppm)35.1.
Embodiment 5
By amidino groups borabenzene ligands lithium salts LiL1 (79.0mg, 0.35mmol) and ScCl
3(THF)
3(133mg, 0.36mmol) mixes, and then adds the tetrahydrofuran (THF) of 5mL-30 DEG C.Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 3mL toluene extracts.By extraction liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane, then vacuum-drying obtains light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] ScCl
2(C1) 100mg, productive rate 85%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.87 (dd,
3j
hH=10.4Hz,
3j
hH=7.4Hz, 2H, 3-/5-H), 6.77 (t,
3j
hH=7.0Hz, 1H, 4-H), 6.52 (m, 2H, 2-/6-H), 3.7-4.7 (br, 1H, CHMe
2), 3.35 (sept,
3j
hH=6.6Hz, 1H, CHMe
2), 1.41 (s, 3H, NC (Me) N), 1.26 (br, 6H, CHMe
2), 0.86 (d,
3j
hH=6.4Hz, 6H, CHMe
2).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 173.0 (NC (Me) N), 142.6,131.2 (br), 116.5 (boratabenzene-C), 49.0,48.1 (CHMe
2), 23.5,22.4,15.2 (NC (Me) NandCHMe
2).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 37.0.C
13h
22bCl
2n
2the Elemental analysis data of Sc: calculated value: C, 46.89; H, 6.66; N, 8.41. measured value: C, 47.19; H, 6.77; N, 8.33.
Embodiment 6
By amidino groups borabenzene ligands lithium salts LiL1 (65.0mg, 0.29mmol) and LuCl
3(90mg, 0.32mmol) mixes, and then adds the tetrahydrofuran (THF) of 5mL-30 DEG C.Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 3mL toluene extracts.By extraction liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane, then vacuum-drying obtains light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] LuCl
2(THF) (C2) 130mg, productive rate 97%.(note: about 90% purity is difficult to purifying, does not affect subsequent reactions.）
1HNMR(400MHz，C
6D
6,25℃):δ(ppm)7.75(dd,
3J
HH=9.8Hz,
3J
HH=7.6Hz,2H,3-/5-H),6.93(d,
3J
HH=9.2Hz,2H,2-/6-H),6.82(t,
3J
HH=6.8Hz,1H,4-H),4.12(br,1H,CHMe
2),3.82(m,4H,THF),3.54(sept,
3J
HH=6.8Hz,1H,CHMe
2),1.67(s,3H,NC(Me)N),1.50(d,
3J
HH=6.8Hz,6H,CHMe
2),1.39(m,4H,THF),1.00(d,
3J
HH=6.4Hz,6H,CHMe
2).
13CNMR(100MHz,C
6D
6,25℃):δ(ppm)170.7(NC(Me)N),138.5,131.8(br),117.8(boratabenzene-C),69.6(THF-C),49.7,47.5(CHMe
2),25.6,24.0,22.5,16.5(THF-C,NC(Me)NandCHMe
2).
11BNMR(128MHz,C
6D
6,25℃):δ(ppm)29.1.
Embodiment 7
By amidino groups borabenzene ligands lithium salts LiL1 (69.0mg, 0.31mmol) and YCl
3(66.0mg, 0.34mmol) mixes, and then adds the tetrahydrofuran (THF) of 5mL-30 DEG C.Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 3mL toluene extracts.By extraction liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane, then vacuum-drying obtains light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] YCl
2(THF) (C3) 110mg, productive rate 96%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.95 (t,
3j
hH=8.4Hz, 2H, 3-/5-H), 7.30 (m, 1H, 4-H), 6.94 (d,
3j
hH=9.6Hz, 2H, 2-/6-H), 4.56 (br, 1H, CHMe
2), 3.25 (sept,
3j
hH=6.6Hz, 1H, CHMe
2), 3.52 (m, 4H, THF), 1.64 (s, 3H, NC (Me) N), 1.45 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 1.38 (m, 4H, THF), 1.00 (d,
3j
hH=6.8Hz, 6H, CHMe
2).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 171.2 (NC (Me) N), 139.9,132.5 (br), 119.5 (br, boratabenzene-C), 70.3 (THF-C), 48.8,47.6 (CHMe
2), 25.4,23.8,22.8,16.4 (THF-C, NC (Me) NandCHMe
2).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 29.2.C
17h
30bCl
2n
2the Elemental analysis data of OY: calculated value: C, 45.47; H, 6.73; N, 6.24. measured value: C, 46.43; H, 6.16; N, 6.29.
Embodiment 8
By amidino groups borabenzene ligands lithium LiL1 (80.0mg, 0.36mmol) and ZrCl
4(84.0mg, 0.36mmol) mixes, and then adds the tetrahydrofuran (THF) of 5mL-30 DEG C.After stirred at ambient temperature reacts 5 minutes, obtain brown color suspension liquid.By this suspension liquid under vacuo except desolventizing, resistates 3 × 3mL toluene extracts.By extraction liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane, then vacuum-drying obtains light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] ZrCl
3(C4) 63.0mg, productive rate 43%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.56 (m, 2H, 4-H), 7.41 (m, 2H, 3-/5-H), 6.64 (m, 2H, 2-/6-H), 4.10 (sept,
3j
hH=6.4Hz, 1H, CHMe
2), 3.25 (sept,
3j
hH=6.5Hz, 1H, CHMe
2), 1.49 (s, 3H, NC (Me) N), 1.21 (d,
3j
hH=6.4Hz, 6H, CHMe
2), 0.73 (d,
3j
hH=6.4Hz, 6H, CHMe
2).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 172.5 (NC (Me) N), 138.8,134.4 (br, boratabenzene-C), 50.3,48.0 (CHMe
2), 23.5,20.9,17.0 (NC (Me) NandCHMe
2).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 37.9.C
13h
22bCl
3n
2the Elemental analysis data of Zr: calculated value: C, 37.65; H, 5.35; N, 6.75. measured value: C, 37.94; H, 5.30; N, 6.82.
Embodiment 9
By amidino groups borabenzene ligands lithium salts LiL1 (67.0mg, 0.30mmol) and CrCl
3(THF)
3(113mg, 0.30mmol) mixes, and then adds the tetrahydrofuran (THF) of 5mL-30 DEG C.After stirred at ambient temperature reacts 10 minutes, obtain blue suspension liquid.By this suspension liquid under vacuo except desolventizing, resistates 3 × 4mL toluene extraction, obtains blue settled solution, and vacuum concentration, to 1.0mL, leaves standstill at-30 DEG C, separates out blue solid.This blue solid toluene wash of 1.0mL-30 DEG C, then use 1.0mL n-hexane, vacuum-drying, obtain blue solid [C
5h
5bN (
ipr) CMeN (
ipr)] CrCl
2(C5) 56mg, productive rate 55%.C
13h
22bCl
2crN
2elemental analysis data: calculated value: C, 45.92; H, 6.52; N, 8.24. measured value: C, 46.13; H, 6.57; N, 8.42.
Embodiment 10
By LiCH
2siMe
3the 1mL tetrahydrofuran solution of (53.0mg, 0.57mmol) is added drop-wise to the scandium amidino groups boron being refrigerated to-30 DEG C and mixes benzene muriate [C
5h
5bN (
ipr) CMeN (
ipr)] ScCl
2in the 3mL tetrahydrofuran solution of (94.0mg, 0.28mmol).Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane extraction.By extraction liquid under vacuo except desolventizing, obtain light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] Sc (CH
2siMe
3)
2(C6) 116mg, productive rate 94%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.95 (t,
3j
hH=9.2Hz, 2H, 3-/5-H), 7.08 (t,
3j
hH=7.6Hz, 1H, 4-H), 6.52 (d,
3j
hH=11.2Hz, 2H, 2-/6-H), 4.10-4.38 (br, 1H, CH (CH
3)
2), 3.40 (sept,
3j
hH=6.4Hz, 1H, CHMe
2), 1.48 (s, 3H, NC (Me) N), 1.24 (d,
3j
hH=6.4Hz, 6H, CHMe
2), 0.95 (d,
3j
hH=6.4Hz, 6H, CHMe
2), 0.29 (s, 9H, SiMe
3), 0.28 (s, 9H, SiMe
3) ,-0.10 (d,
2j
hH=10.8Hz, 2H, CH
2siMe
3) ,-0.26 (d,
2j
hH=11.2Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.9 (NC (Me) N), 139.9,131.1 (br), 115.5 (boratabenzene-C), 48.4,47.8,42.7 (CH
2siMe
3andCHMe
2), 23.7,23.5,15.2 (NC (Me) NandCHMe
2), 4.1 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 35.9.C
21h
44bN
2scSi
2elemental analysis data: calculated value: C, 57.78; H, 10.16; N, 6.42. measured value: C, 57.54; H, 10.10; N, 6.55.
Embodiment 11
By LiCH
2siMe
3the 1mL tetrahydrofuran solution of (41.0mg, 0.44mmol) is added drop-wise to the lutetium amidino groups boron being refrigerated to-30 DEG C and mixes benzene muriate [C
5h
5bN (
ipr) CMeN (
ipr)] LuCl
2(THF) in the 3mL tetrahydrofuran solution of (100mg, 0.22mmol).Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane extraction.By extraction liquid under vacuo except desolventizing, obtain light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] Lu (CH
2siMe
3)
2(C7) 104mg, productive rate 85%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.88 (dd,
3j
hH=10.0,
3j
hH=7.2Hz, 2H, 3-/5-H), 6.92 (tt,
3j
hH=7.6Hz,
4j
hH=1.2Hz, 1H, 4-H), 6.40 (dd,
3j
hH=10.8Hz,
4j
hH=1.2Hz, 2H, 2-/6-H), 3.40 (sept,
3j
hH=6.5Hz, 2H, CHMe
2), 1.36 (s, 3H, NC (Me) N), 1.31 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.94 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.31 (s, 18H, SiMe
3) ,-0.69 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.84 (m,
2j
hH=11.2Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.8 (NC (Me) N), 139.1,130.5 (br), 114.3 (boratabenzene-C), 48.9,47.7,41.3 (CH
2siMe
3andCHMe
2), 23.8,23.3,13.3 (NC (CH
3) NandCH (CH
3)
2), 4.2 (Si (CH
3)
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.0.C
21h
44bLuN
2si
2elemental analysis data: calculated value: C, 44.52; H, 7.83; N, 4.94. measured value: C, 44.44; H, 8.09; N, 4.96.
Embodiment 12
By LiCH
2siMe
3the 1mL tetrahydrofuran solution of (45.0mg, 0.48mmol) is added drop-wise to the yttrium amidino groups boron being refrigerated to-30 DEG C and mixes benzene muriate [C
5h
5bN (
ipr) CMeN (
ipr)] YCl
2(THF) in the 3mL tetrahydrofuran solution of (106mg, 0.24mmol).Stirred at ambient temperature obtains yellow suspension after reacting 5 minutes.By this suspension liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane extraction.By extraction liquid under vacuo except desolventizing, obtain light yellow solid [C
5h
5bN (
ipr) CMeN (
ipr)] Y (CH
2siMe
3)
2(C8) 91mg, productive rate 81%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.84 (dd,
3j
hH=9.2Hz,
3j
hH=7.6Hz, 2H, 3-/5-H), 6.93 (t,
3j
hH=7.2Hz, 1H, 4-H), 6.42 (d,
3j
hH=10.0Hz, 2H, 2-/6-H), 3.46 (sept,
3j
hH=6.5Hz, 1H, CHMe
2), 3.22 (sept,
3j
hH=6.7Hz, 1H, CHMe
2), 1.40 (s, 3H, NC (Me) N), 1.30 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.96 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.23 (s, 18H, SiMe
3) ,-0.61 (m, 2H, CH
2siMe
3) ,-0.69 (m, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.6 (NC (Me) N), 139.0,131.2 (br), 114.7 (boratabenzene-C), 49.6,48.0,35.4,35.0 (CH
2siMe
3andCHMe
2), 25.1,23.8,13.2 (NC (Me) NandCHMe
2), 4.5 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.1.C
21h
44bN
2si
2the Elemental analysis data of Y: calculated value: C, 52.49; H, 9.23; N, 5.83. measured value: C, 51.54; H, 8.93; N, 5.63.
Embodiment 13
By the 1mL tetrahydrofuran (THF) dilution of the methylene diethyl ether solution (0.16mL, 3mol/L, 0.48mmol) of LiMe, and be added drop-wise to [the C being refrigerated to-30 DEG C
5h
5bN (
ipr) CMeN (
ipr)] CrCl
2in the 3mL tetrahydrofuran solution of (82.0mg, 0.24mmol).After stirred at ambient temperature reacts 5 minutes, obtain brownish black suspension liquid.By this suspension liquid under vacuo except desolventizing, resistates 3 × 2mL n-hexane extraction.By extraction liquid under vacuo except desolventizing, obtain brownish black solid [C
5h
5bN (
ipr) CMeN (
ipr)] CrMe
2(C9) 110mg, productive rate 84%.C
15h
28bCrN
2elemental analysis data: calculated value: C, 60.21; H, 9.43; N, 9.36. measured value: C, 60.37; H, 9.59; N, 9.05.
Embodiment 14
By amidino groups borabenzene ligands sylvite KL2 (142mg, 0.50mmol) and ScCl
3(THF)
2(189mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.By this suspension liquid under vacuo except desolventizing, then add alkyl lithium salts (94.5mg, 1mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction.Yellow extraction liquid is concentrated into 1mL under vacuo, then leaves standstill at-30 DEG C, separate out yellow solid.This yellow solid 0.5mL-30 DEG C of n-hexane, vacuum-drying obtains yellow solid [(Me)
2c
5h
3bN (
ipr) CMeN (
ipr)] Sc (CH
2siMe
3)
2(C10) 120mg, productive rate 52%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 6.72 (s, 1H, 4-H), 6.00 (s, 2H, 2-/6-H), 4.13 (br, 1H, CHMe
2), 3.44 (sept,
3j
hH=6.4Hz, 1H, CHMe
2), 2.40 (s, 6H, 3-/5-Me), 1.50 (s, 3H, NC (Me) N), 1.36 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.99 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.30 (s, 18H, SiMe
3) ,-0.11 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.19 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.3 (NC (Me) N), 151.3,118.4 (boratabenzene-C), 48.7,47.8,42.7 (CHMe
2andCH
2siMe
3), 26.4,24.1,23.7,14.7 (3-/5-Me, NC (Me) NandCHMe
2), 4.3 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.2.C
23h
48bN
2scSi
2elemental analysis data: calculated value: C, 59.46; H, 10.41; N, 6.03. measured value: C, 59.24; H, 10.33; N, 5.45.
Embodiment 15
By amidino groups borabenzene ligands sylvite KL2 (142mg, 0.50mmol) and LuCl
3(141mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.By this suspension liquid under vacuo except desolventizing, then add alkyl lithium salts (94.2mg, 1.00mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction.Yellow extraction liquid is concentrated into 1mL under vacuo, then leaves standstill at-30 DEG C, separate out light yellow solid.This solid 0.5mL-30 DEG C of hexanes wash, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (
ipr) CMeN (
ipr)] Lu (CH
2siMe
3)
2(C11) 208mg, productive rate 70%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 6.58 (s, 1H, 4-H), 6.06 (s, 2H, 2-/6-H), 3.44 (sept,
3j
hH=6.4Hz, 2H, CHMe
2), 2.41 (s, 6H, 3-/5-Me), 1.41 (s, 3H, NC (Me) N), 1.39 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.99 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.32 (s, 18H, SiMe
3) ,-0.66 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.87 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.7 (NC (Me) N), 150.7,117.1 (boratabenzene-C), 49.4,48.1,41.9 (CHMe
2andCH
2siMe
3), 26.2,24.2,23.7,13.6 (3-/5-Me, NC (Me) NandCHMe
2), 4.8 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.7.C
23h
48bLuN
2si
2elemental analysis data: calculated value: C, 46.46; H, 8.14; N, 4.71. measured value: C, 45.99; H, 8.01; N, 4.45.
Embodiment 16
By amidino groups borabenzene ligands sylvite KL3 (182mg, 0.50mmol) and ScCl
3(THF)
3(189mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.This suspension liquid is under vacuo except desolventizing, add alkyl lithium salts (94.2mg again, 1.00mmol) with 10mL toluene, after stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction, for yellow clear solution, vacuum concentration to 0.5mL, then leaves standstill at-30 DEG C, separates out light yellow solid.This solid 0.5mL-30 DEG C of n-hexane, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (Cy) CMeN (Cy)] Sc (CH
2siMe
3)
2(C12) 160mg, productive rate 59%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 6.74 (s, 1H, 4-H), 6.03 (s, 2H, 2-/6-H), 3.45 (br, 1H, CH
2cHCH
2), 3.18 (m, 1H, (CH
2) CH (CH
2)), 2.45 (s, 6H, 3-/5-Me), 2.00 ~ 0.76 (m, 20H, (CH
2)
5), 1.61 (s, 3H, NC (Me) N), 0.30 (s, 18H, SiMe
3) ,-0.02 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.14 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.0 (NC (Me) N), 151.4,128.6,118.4 (boratabenzene-C), 59.0,56.8,43.4 ((CH
2) CH (CH
2) andCH
2siMe
3), 34.9,34.4,26.5,26.1,25.6,25.5,14.0 (3-/5-Me, NC (Me) Nand (CH
2)
5), 4.3 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 35.7.C
29h
56bN
2scSi
2elemental analysis data: calculated value: C, 63.94; H, 10.36; N, 5.14. measured value: C, 63.94; H, 10.59; N, 4.92.
Embodiment 17
By amidino groups borabenzene ligands sylvite KL3 (182mg, 0.50mmol) and LuCl
3(141mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.This suspension liquid under vacuo except desolventizing, then adds alkyl lithium salts (94.2mg, 1.00mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction.This light yellow extraction liquid is concentrated into 1mL under vacuo, then leaves standstill at-30 DEG C, separate out light yellow solid.This solid 0.5mL-30 DEG C of n-hexane, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (Cy) CMeN (Cy)] Lu (CH
2siMe
3)
2(C13) 223mg, productive rate 66%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 6.60 (s, 1H, 4-H), 6.07 (s, 2H, 2-/6-H), 3.18 (m, 2H, (CH
2) CH (CH
2)), 2.44 (s, 6H, 3-/5-Me), 2.06 ~ 0.77 (m, 20H, (CH
2)
5), 1.53 (s, 3H, NC (Me) N), 0.33 (s, 18H, SiMe
3) ,-0.62 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.83 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.6 (NC (Me) N), 150.7,116.9 (boratabenzene-C), 59.0,56.9,41.9 ((CH
2) CH (CH
2) andCH
2siMe
3), 34.8,34.7,26.3,26.1,25.9,25.4,25.3,13.5 (3-/5-Me, NC (Me) Nand (CH
2)
5), 4.8 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.8.C
29h
56bLuN
2si
2elemental analysis data: calculated value: C, 51.62; H, 8.37; N, 4.15. measured value: C, 51.59; H, 8.50; N, 4.00.
Embodiment 18
By amidino groups borabenzene ligands sylvite KL3 (182mg, 0.50mmol) and YCl
3(98.0mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.After stirring at room temperature reacts 25 minutes, obtain light yellow suspension liquid.This suspension liquid under vacuo except desolventizing, then adds alkyl lithium salts (94.2mg, 1.00mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction, is light yellow settled solution, and vacuum concentration to 0.5mL, then leaves standstill at-30 DEG C, separates out light yellow solid.This solid 0.5mL-30 DEG C of n-hexane, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (Cy) CMeN (Cy)] Y (CH
2siMe
3)
2(C14) 179mg, productive rate 61%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 6.64 (s, 1H, 4-H), 6.15 (s, 2H, 2-/6-H), 3.16 (m, 1H, (CH
2) CH (CH
2)), 3.03 (m, 1H, (CH
2) CH (CH
2)), 2.44 (s, 6H, 3-/5-Me), 2.12 ~ 0.76 (m, 20H, (CH
2)
5), 1.51 (s, 3H, NC (Me) N), 0.34 (s, 18H, SiMe
3) ,-0.48 (dd,
2j
hH=11.6Hz,
2j
yH=2.8Hz, 2H, CH
2siMe
3) ,-0.59 (dd,
2j
hH=11.6Hz,
2j
yH=3.2Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 170.0 (d, J
y-C=1.9Hz, NC (Me) N), 150.5,117.2 (boratabenzene-C), 59.2,56.9 ((CH
2) CH (CH
2)), 35.9 (d, J
y-C=38.0Hz, CH
2siMe
3), 35.9,35.7,34.8,26.3,26.1,25.8,25.4,25.3,13.2 ((3-/5-Me, NC (Me) Nand (CH
2)
5), 4.6 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 37.3.C
29h
56bN
2si
2the Elemental analysis data of Y: calculated value: C, 59.17; H, 9.59; N, 4.76. measured value: C, 58.98; H, 9.59; N, 4.79.
Embodiment 19
By amidino groups borabenzene ligands sylvite KL4 (173.mg, 0.50mmol) and ScCl
3(THF)
3(189mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.By this suspension liquid under vacuo except desolventizing, then add alkyl lithium salts (94.2mg, 1.00mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction.Yellow extraction liquid is concentrated into 0.5mL under vacuo, then leaves standstill at-30 DEG C, separate out light yellow solid.This solid 0.5mL-30 DEG C of n-hexane, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (
ipr) CPhN (
ipr)] Sc (CH
2siMe
3)
2(C15) 160mg, productive rate 61%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.10 (m, 5H, Ph-H), 6.85 (s, 1H, 4-H), 6.29 (s, 2H, 2-/6-H), 3.35 (sept,
3j
hH=6.8Hz, 1H, CHMe
2), 3.25 (sept,
3j
hH=6.4Hz, 1H, CHMe
2), 2.48 (s, 6H, 3-/5-Me), 1.30 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.99 (d,
3j
hH=7.2Hz, 6H, CHMe
2), 0.35 (s, 18H, SiMe
3), 0.12 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.02 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 172.6 (NC (Me) N), 151.5,134.7,129.3,129.1,129.0,126.8,119.2 (boratabenzene-CandPh-C), 51.0,49.3,46.0 (CHMe
2andCH
2siMe
3), 26.4,24.8,23.6 (3-/5-MeandCHMe
2), 4.5 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.4.C
28h
50bN
2scSi
2elemental analysis data: calculated value: C, 63.86; H, 9.57; N, 5.32. measured value: C, 63.97; H, 9.56; N, 5.13.
Embodiment 20
By amidino groups borabenzene ligands sylvite KL4 (173mg, 0.50mmol) and LuCl
3(141mg, 0.50mmol) mixes, and then adds the tetrahydrofuran (THF) of 10mL-30 DEG C.Stirring at room temperature obtains yellow suspension after reacting 25 minutes.By this suspension liquid under vacuo except desolventizing, then add alkyl lithium salts (94.2mg, 1.00mmol) and 10mL toluene.After stirring at room temperature reacts 10 minutes, solvent removed in vacuo, then uses 3 × 5mL n-hexane extraction.Yellow extraction liquid is concentrated into 1mL under vacuo, then leaves standstill at-30 DEG C, separate out light yellow solid.This solid 0.5mL-30 DEG C of n-hexane, then vacuum-drying obtains light yellow solid [(Me)
2c
5h
3bN (
ipr) CPhN (
ipr)] Lu (CH
2siMe
3)
2(C16) 224mg, productive rate 68%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.06 (m, 5H, Ph-H), 6.67 (s, 1H, 4-H), 6.32 (s, 2H, 2-/6-H), 3.27 (sept,
3j
hH=6.8Hz, 2H, CHMe
2), 2.46 (s, 6H, 3-/5-Me), 1.24 (d,
3j
hH=6.4Hz, 6H, CHMe
2), 0.98 (d,
3j
hH=6.8Hz, 6H, CHMe
2), 0.36 (s, 18H, SiMe
3) ,-0.57 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3) ,-0.79 (d,
2j
hH=11.6Hz, 2H, CH
2siMe
3).
13cNMR (100MHz, C
6d
6, 25 DEG C): δ (ppm) 173.3 (NC (Me) N), 150.8,134.4,129.2,129.1,126.8,117.5 (boratabenzene-CandPh-C), 50.3,49.5,43.5 (CHMe
2andCH
2siMe
3), 26.2,24.6,23.6 (3-/5-MeandCHMe
2), 4.9 (SiMe
3).
11bNMR (128MHz, C
6d
6, 25 DEG C): δ (ppm) 36.8.C
28h
50bLuN
2si
2elemental analysis data: calculated value: C, 51.21; H, 7.67; N, 4.21. measured value: C, 51.43; H, 7.82; N, 4.00.
Embodiment 21
By amidino groups borabenzene ligands sylvite KL3 (110mg, 0.30mmol) and ZrCl
4(70.0mg, 0.30mmol) mixes, and then adds the tetrahydrofuran (THF) of 6mL-30 DEG C.Stirring at room temperature is reacted, and along with the carrying out of reaction, reaction solution adularescent suspension liquid gradually becomes yellow suspension, and after 10 minutes, solvent removed in vacate, then uses 3 × 3mL toluene to extract, obtain yellow clear solution.This clear liquid is concentrated into 0.5mL under vacuo, more freezing at-30 DEG C, separates out yellow solid.This yellow solid 0.5mL-30 DEG C of toluene wash, then use 1mL n-hexane, vacuum-drying, obtain yellow solid [(Me)
2c
5h
3bN (Cy) CMeN (Cy)] ZrCl
3(C17) 81.0mg, productive rate 53%.
1hNMR (400MHz, C
6d
6, 25 DEG C): δ (ppm) 7.31 (s, 1H, 4-H), 6.42 (s, 2H, 2-/6-H), 3.65 (m, 1H, (CH
2) CH (CH
2)), 3.04 (m, 1H, (CH
2) CH (CH
2)), 2.45 (s, 6H, 3-/5-Me), 1.60 ~ 0.66 (m, 20H, (CH
2)
5), 1.70 (s, 3H, NC (Me) N) .C
21h
34bCl
3n
2the Elemental analysis data of Zr: calculated value: C, 48.64; H, 6.55; N, 536. measured values: C, 48.58; H, 6.87; N, 5.11.
Embodiment 22
By amidino groups borabenzene ligands sylvite KL2 (85.5mg, 0.30mmol) and CrCl
3(THF)
3(113mg, 0.30mmol) mixes, and then adds the tetrahydrofuran (THF) of 8mL-30 DEG C.Stirring at room temperature is reacted, and along with the carrying out of reaction, reaction solution adularescent suspension liquid gradually becomes blackish green suspension liquid, and after 10 minutes, solvent removed in vacate, then uses 3 × 3mL toluene to extract, obtain blue settled solution.This clear liquid is concentrated into 1.5mL under vacuo, then leaves standstill at-30 DEG C, separates out blue solid.This blue solid uses 3 × 2mL toluene to extract again, and extraction liquid is concentrated into 1mL under vacuo, leaves standstill at-30 DEG C, separates out blue solid.This blue solid 0.5mL-30 DEG C of toluene wash, then use 1mL n-hexane, vacuum-drying, obtain blue solid [(Me)
2c
5h
3bN (
ipr) CCH
3n (
ipr)] CrCl
2(C18) 51.0mg, productive rate 48%.C
15h
26bCl
2crN
2the Elemental analysis data of 0.25toluene: calculated value: C, 51.44; H, 7.22; N, 7.16. measured value: C, 51.45; H, 6.87; N, 7.34.
Embodiment 23
By amidino groups borabenzene ligands sylvite KL3 (110mg, 0.30mmol) and CrCl
3(THF)
3(113mg, 0.30mmol) mixes, and then adds the tetrahydrofuran (THF) of 8mL-30 DEG C.Stirring at room temperature is reacted, and along with the carrying out of reaction, reaction solution adularescent suspension liquid gradually becomes blue suspension liquid, and after 10 minutes, solvent removed in vacate, then uses 3 × 5mL toluene to extract, obtain blue settled solution.This clear liquid is concentrated into 1mL under vacuo, more freezing at-30 DEG C, separates out blue solid.This blue solid 0.5mL-30 DEG C of toluene wash, then use 1mL n-hexane, vacuum-drying, obtain blue solid [(Me)
2c
5h
3bN (Cy) CMeN (Cy)] CrCl
2(C19) 80.0mg, productive rate 59%.C
21h
34bCl
2crN
2the Elemental analysis data of 0.25toluene: calculated value: C, 57.98; H, 7.70; N, 5.94. measured value: C, 57.79; H, 7.48; N, 6.15.
Embodiment 24
By amidino groups borabenzene ligands sylvite KL4 (104mg, 0.30mmol) and CrCl
3(THF)
3(113mg, 0.30mmol) mixes, and then adds the tetrahydrofuran (THF) of 8mL-30 DEG C.Stirring at room temperature is reacted, and along with the carrying out of reaction, reaction solution adularescent suspension liquid gradually becomes blackish green suspension liquid, and after 10 minutes, solvent removed in vacate, then uses 3 × 3mL toluene to extract, obtain blue settled solution.This clear liquid is concentrated into 1.5mL under vacuo, then leaves standstill at-30 DEG C, separates out blue solid.This blue solid 0.5mL-30 DEG C of toluene wash, then use 1mL n-hexane, vacuum-drying, obtain blue solid [(Me)
2c
5h
3bN (
ipr) CPhN (
ipr)] CrCl
2(C20) 64.0mg, productive rate 50%.C
20h
28bCl
2crN
2elemental analysis data: calculated value: C, 55.84; H, 6.56; N, 6.51. measured value: C, 55.28; H, 6.48; N, 6.00.
Embodiment 25
Add 30mL toluene and Al being connected with in an atmospheric vinyl polymerization bottle
ibu
3toluene solution, be then placed in 30 DEG C of oil bath constant temperature certain hours.Mix amidino groups boron benzene early transition metal title complex C6-C8, C10-C16(10 μm of ol) 1mL toluene solution join activator [Ph
3c] [B (C
6f
5)
4] (10 μm of ol) 9mL toluene solution in, stir a moment, rapidly this mixing solutions joined in vinyl polymerization bottle, stir after 5min, by the acidic ethanol termination reaction of 5%.Polymkeric substance is after precipitation, filtration, washing, and vacuum-drying is to weight.Vinyl polymerization result is as following table.
Note: Complex: amidino groups boron is mixed benzene rare earth metal complex; Equiv.: equivalent; Temp.: temperature; Activity: active, unit is KgPE/molLnhatm; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Embodiment 26
Be connected with the n-heptane solution adding 39mL toluene and MMAO in an atmospheric vinyl polymerization bottle, be then placed in 30 DEG C of oil bath constant temperature certain hours.Mix amidino groups boron benzene early transition metal title complex C4, C5, C17-C20(1 μm of ol) 1mL toluene solution join in vinyl polymerization bottle, stir after 3min, by the acidic ethanol termination reaction of 5%.Polymkeric substance is after precipitation, filtration, washing, and vacuum-drying is to weight.Vinyl polymerization result is as following table.
Note: Complex: amidino groups boron is mixed benzene rare earth metal complex; MMAO: the methylaluminoxane of modification; Equiv.: equivalent; Temp.: temperature; Activity: active, unit is KgPE/molCrhatm; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Embodiment 27
Add 30mL toluene and Al being connected with in an atmospheric vinyl polymerization bottle
ibu
3toluene solution, 1-hexene (1-Hexene), be then placed in 30 DEG C of oil bath constant temperature certain hours.Mix amidino groups boron benzene early transition metal title complex C12(10 μm of ol) 1mL toluene solution join activator [Ph
3c] [B (C
6f
5)
4] (10 μm of ol) 9mL toluene solution in, stir a moment, rapidly this mixing solutions joined in vinyl polymerization bottle, stir after 5min, by the acidic ethanol termination reaction of 5%.Polymkeric substance is after precipitation, filtration, washing, and vacuum-drying is to weight.Vinyl polymerization result is as following table.
Note: equiv.: equivalent; Temp.: temperature; Activity: active, unit is KgPoly./molSchatm; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Embodiment 28
Being connected with the n-heptane solution, the 1-hexene (1-Hexene) that add 39mL toluene and MMAO in an atmospheric vinyl polymerization bottle, be then placed in 30 DEG C of oil bath constant temperature certain hours.Mix amidino groups boron benzene early transition metal title complex C5 and C18(1 μm of ol) 1mL toluene solution join in vinyl polymerization bottle, stir after 3min, by the acidic ethanol termination reaction of 5%.Polymkeric substance is after precipitation, filtration, washing, and vacuum-drying is to weight.Vinyl polymerization result is as following table.
Note: Complex: amidino groups boron is mixed benzene rare earth metal complex; MMAO: the methylaluminoxane of modification; Equiv.: equivalent; Temp.: temperature; Activity: active, unit is KgPE/molCrhatm; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Claims (12)
1. a class is mixed based on amidino groups boron the early transition metal title complex of phenyl ligands, it is characterized in that having following structural formula:
In structure above:
M is Sc or Cr ion;
R
1, R
3and R
5for H; R
2and R
4for the alkyl of H or C1 ~ C4; R
6and R
8for C1-C8 alkyl; R
7for the alkyl or phenyl of C1-C4;
X: be halogen, the alkyl of C1 ~ C4 or C1 ~ C4 alkyl of silicon C1 ~ C6 alkyl replacement;
for coordinate bond;
N is 2.
2. a class as described in claim 1 is mixed based on amidino groups boron the early transition metal title complex of phenyl ligands,
It is characterized in that there is following structural formula:
In structure above, R
6, R
7, R
8, M, X, n,
as claimed in claim 1.
3. a class as described in claim 1 is mixed based on amidino groups boron the early transition metal title complex of phenyl ligands, and it is characterized in that described amidino groups borabenzene ligands, structural formula is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8identical with described in aforementioned claim 1.
4. a class as described in claim 2 is mixed based on amidino groups boron the early transition metal title complex of phenyl ligands, and it is characterized in that described amidino groups borabenzene ligands, structural formula is as follows:
Wherein, R
6, R
7and R
8identical with described in aforementioned claim 1.
5. an amidino groups boron as claimed in claim 1 is mixed the preparation method of benzene early transition metal title complex, it is characterized in that in organic solvent and at-70 ~ 50 DEG C, react 5 ~ 60min by the halogenide of amidino groups borabenzene ligands an alkali metal salt and Sc or Cr with mol ratio 1:0.1 ~ 6, obtaining X is that the amidino groups boron of halogen is mixed benzene early transition metal title complex;
Described basic metal is Li or K; Described amidino groups borabenzene ligands has following structural formula:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8definition is with described in claim 1;
In organic solvent and at-70 ~ 50 DEG C, the amidino groups boron being halogen by above-mentioned acquisition X benzene early transition metal title complex of mixing reacts 5 ~ 60min with lithium reagent with mol ratio 1:0.1 ~ 6 again and synthesizes, and obtaining X is that the amidino groups boron of alkyl is mixed benzene early transition metal title complex;
Described lithium reagent is the hydrocarbyl lithium of C1 ~ C4 or C1 ~ C4 lithium alkylide of silicon C1 ~ C6 alkyl replacement;
Described amidino groups boron benzene early transition metal title complex of mixing has following structural formula:
Wherein, M, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8,
with the definition of n with described in claim 1.
6. amidino groups boron as claimed in claim 5 is mixed the preparation method of benzene early transition metal title complex, it is characterized in that described organic solvent is tetrahydrofuran (THF).
7. amidino groups boron as claimed in claim 5 is mixed the preparation method of benzene early transition metal title complex, it is characterized in that described organic solvent is tetrahydrofuran (THF) or toluene.
8. amidino groups boron as claimed in claim 5 is mixed the preparation method of benzene early transition metal title complex, and its feature early transition metal is Sc or Cr; Described X is chlorine.
9. an amidino groups boron as claimed in claim 1 is mixed the purposes of benzene early transition metal title complex, it is characterized in that under promotor exists, or activator and promotor jointly in the presence of for catalysis in olefine polymerization, described olefinic polymerization refers to homopolymerization or copolymerization, and described alkene refers to ethene or C
3-C
6alpha-olefin.
10. amidino groups boron as claimed in claim 9 is mixed the purposes of benzene early transition metal title complex, it is characterized in that described activator is [Ph
3c] [B (C
6f
5)
4], [PhNMe
2h] [B (C
6f
5)
4] or B (C
6f
5)
3boride; Described promotor is methylaluminoxane, isobutyl aluminium alkoxide, the methylaluminoxane of modification or AlR
3, R be Me base, Et base,
ibu base or CH
2siMe
3base.
11. amidino groups boron as described in claim 9 or 10 are mixed the purposes of benzene early transition metal title complex, it is characterized in that in organic solvent toluene, catalysis in olefine polymerization under-20 ~ 100 DEG C of conditions.
12. amidino groups boron as claimed in claim 9 are mixed the purposes of benzene early transition metal title complex, it is characterized in that described homopolymerization is ethylene homo, copolymerization is ethene and the copolymerization of alpha-olefin.
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| CN102603810A (en) * | 2012-01-29 | 2012-07-25 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method of rare earth complex, catalysis system for polymerization and preparation method of catalysis system, and preparation method of polymer |
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| CN102603810A (en) * | 2012-01-29 | 2012-07-25 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method of rare earth complex, catalysis system for polymerization and preparation method of catalysis system, and preparation method of polymer |
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