CN1146569C - Dialkylmethylene bridged fluorenyl cyclopentadiene rare-earth complex and its preparing process and application - Google Patents

Abstract

The present invention relates to a dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl alkene compound having the following molecular formula, a synthesis method and a catalyst application: {[(X ¹ ) ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )]MX ² (L) _n } _m , wherein R ¹ , R ³ or R ⁴ ＝H or CH ₃ , R ² ＝H or C _1-4 R ⁵ or R ⁶ ＝H, C _1-4 alkyl or Si(CH ₃ ) ₃ , R ⁷ ＝Si, C, Ge or Sn, X ¹ ＝C _1-4 alkyl or benzene group, X ² =Cl, BH ₄ , H, C _1-4 alkyl, N[(CH ₃ ) ₃ Si] ₂ , CH[(CH ₃ ) ₃ Si] ₂ , CH ₂ [(CH ₃ ) ₃ Si] or tetrahydrofuran (THF), M=lanthanides, yttrium or scandium, L=(CH ₃ ) ₃ Si, Li(THF) ₄ , [Y-crown ether] or [Y-crown ether]-2,4 - Hexacyclic epoxy ring, n=1 or 0, m=1 or 2, when m=2, n=0, Y=monovalent metal, crown ether=18-crown ether-6 or 15-crown ether-5 .

Description

A dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex, its synthesis method and application

The invention relates to rare earth organic chemistry, in particular to a phenylmethylene bridging fluorenyl cyclopentadienyl rare earth complex, a synthesis method and an application as a polymerization reaction catalyst.

Organometallic chemistry and catalysis are one of the frontiers of contemporary chemistry, and organometallic chemistry of rare earth elements has received special attention. Lanthanides include fifteen elements with atomic numbers from 57 to 71. Scandium and yttrium are similar to lanthanides according to their properties and coexist with them in nature. These 17 elements are collectively called rare earth elements. Since the 4f orbital of rare earth metals is in the inner layer compared with the normal valence electron orbitals 6s, 6p, and 5d, it has a greater shielding effect, has weaker interactions with ligand orbitals, and has a relatively low bonding ability. Therefore, rare earth metal organic chemistry development has been sluggish for a while. With the continuous development of modern experimental techniques and analysis methods, rare earth organic compounds can be synthesized and identified according to conventional reactions. In the late 1970s, the research on rare earth organic compounds was rapidly developed. First, several types of rare earth compounds with the characteristic valence state Ln ³⁺ of the rare earth element series were discovered, and then extended to Ln ⁰ , Ln ²⁺ , Rare earth elements in Ln ⁴⁺ oxidation state. These organometallic compounds are used in organic synthesis as typical reagents or as highly active catalysts. Rare earth metal organic chemistry shows potential application prospects.

Rare earth organic compounds play an important role in homogeneously catalyzing the formation of C-H, C-C, and C-X bonds. Currently, most of the work on rare-earth organic compounds is stabilized by cyclopentadienyl or its analogues, where alkyl compounds or hydrides both show high activity as catalysts or stoichiometric reactants. Generally, linking cyclopentadienyl ligands or changing substituents on them can significantly improve its catalytic activity. For metal complexes, the coordination environment is very important to their reactivity, especially for rare earth metal complexes, since the 4f valence orbital is greatly shielded by the inner orbital, when it forms a bond with the ligand, electrostatic factors and The steric factor is often more important than the inter-orbital interactions, so the coordination environment plays a decisive role in its reactivity. The properties of the complexes it forms are quite different from those of the d-block complexes, so the rare earth metal complexes have their own unique structures and reactivity. Due to the limited expansion of the 4f orbital, its role in rare earth complexes is not as large as that of the d orbital in transition metals, so the influence of ligands becomes more important. To fully exploit the rare earth reaction chemistry, it is necessary to effectively tune the coordination environment of the ligands around the metal.

Cyclopentadienyl ligands have played an important role in rare earth organochemistry until now. Cyclopentadienyl is considered as an auxiliary ligand in chlorides, and generally it does not participate in the reaction. The Cp group can improve the solubility and stability of chlorides, making it possible to study the chemical reaction of the Ln-Z bond. Dicene chlorides are important precursors for the synthesis of rare earth metal organic complexes containing Ln-C, Ln-H and Ln-N bonds. In 1980, Evans et al. synthesized [(CH ₃ ) ₅ C ₅ ] ₂ Nd(μ-Cl) ₂ Li(THF) ₂ rare earth complexes using pentamethylcyclopentadiene with a relatively large steric hindrance as a ligand ( Inorg. Chem., 19, 2190, 1980). Since then, pentamethylcyclopentadiene has become the most commonly used ligand, far surpassing the previously used unsubstituted cyclopentadienyl, and the research on rare earth dioxocene complexes has been greatly developed. In 1981, using C ₅ H ₃ (SiMe ₃ ) ₂ as a ligand, Lappert successfully synthesized a stable light rare earth dioxocene complex {Ln[C ₅ H ₂ (SiMe ₃ ) ₂ ] ₂ Cl} and [C ₅ H ₂ (SiMe ₃ ) ₂ ] ₂ Ln(μ-Cl ₂ )Li(THF) ₂ (Ln=La, Pr, Nd), and their Crystal structure (J. Chem. Soc., Chem. Commun., 1190, 1981).

Bridged dicyclopentadiene is an ideal ligand for stabilizing light rare earth cyanochlorides. Due to the bridging effect, the degree of freedom of the ringocene ring is reduced, and the geometric structure of the metallocene is changed. Some parts around the metal are relatively crowded, and other parts are relatively loose. The complex is not only stabilized, but the central metal ion also has a larger reaction contact surface. Such complexes become a class of catalysts with extremely high catalytic activity. In particular, the single-atom bridged dicene ligand can expand the space around the metal ion more, the reaction substrate is more accessible to the central metal ion, and the reactivity is enhanced. In 1980, we cooperated with Tsutsui and successfully synthesized light rare earth chlorides and hydrocarbon rare earth complexes containing σ-bonds by using C ₅ H ₅ CH ₂ CH ₂ CH ₂ C ₅ H ₅ as ligands, effectively avoiding light Disproportionation reaction of rare earth complexes (J. Organomet Chem., 263, 333, 1984). Subsequently, a series of novel bridging ligands were developed, such as C ₅ H ₅ CH ₂ C ₆ H ₄ CH ₂ C ₅ H ₅ , C ₅ H ₅ CH ₂ CH ₂ OCH ₂ C ₅ H ₅ and C ₅ H ₅ CH ₂ CH ₂ NCH ₃ CH ₂ CH ₂ C ₅ H ₅ , they better stabilize the light rare earth dicene chlorides, and the corresponding rare earth complexes also have higher reactivity (J.Organomet.Chem., 299.97, 1986 ; Inorganic Chimica Acta, 139, 195, 1987; L Polyhydron, 9, 479, 1990)

In recent years, it has been reported that rare earth metallocene complexes can be used as catalysts for active polymerization of polar and non-polar monomers, and polymers with high molecular weight and narrow molecular weight distribution can be obtained, although two-component and three-component Catalytic systems are still widely used in polymerization reactions, and it will be possible to replace them with one-component catalytic systems in the near future (H. Yasuda et al., Bull. Chem. Soc. Jpn., 70, 1745, 1977).

As the fourth subgroup metallocene catalysts are used in olefin polymerization, the activity of rare earth metallocene complexes on ethylene, α-olefins, polar monomers and many organic reactions has made people have a great deal of interest in it. interest of. The catalytic system of the fourth subgroup contains a variety of ligands of cyclopentadienyl derivatives. For example, cyclocene, substituted cyclocene, indenyl and fluorenyl, etc. In contrast, the synthetic methods of rare earth metallocenes are very limited. This is mainly due to the strong Lewis acidity, large ionic radius and low covalent bonding of rare earth metal ions, which make the rare earth complexes unstable and prone to disproportionation reactions or complex solvent molecules at the metal center, reducing the reactivity. . In order to overcome these problems and further understand the role of π-ligands in the control of the overall molecular geometry and electrical properties in rare earth complexes, fluorenyl ligands are used in the polymerization of alkenes in metallocene catalyst systems with cyclocene substituents. unique role in the reaction. Only the synthesis and structure of bisfluorenyl bivalent samarium complexes (W.J.Evani. et al., Organometallics, 13, 1281, 1994) and the synthesis of trivalent yttrium and lanthanum polyfluorenyl complexes have been reported in the current literature. The structure of the latter has not been determined (R.K. Sharma et al., J.Indian Chem.Soc., 64, 506, 1987). The synthesis, structure and catalytic activity of rare earth complexes containing fluorenyl ligands have not been elucidated properly.

The reaction of Cs-symmetry rare earth complexes to catalyze MIMA polymerization has not been reported yet. Combined with the expansion of our research work on the synthesis of bridging organic rare earth metallocene complexes, taking into account various factors such as different bridging atoms and substituents For the possible impact on the structural reactivity of the complexes, a single-atom bridged fluorenylcyclopentadienyl rare earth complex with Cs-symmetry was designed and synthesized. It is hoped to characterize their structural properties, investigate their activity in catalyzing the polymerization of α-olefins and polar monomers, and further understand the influence of the structure of organic rare earth metallocene complexes on the microstructure of polymers. It not only has certain significance for enriching the chemistry of rare earth complexes, but also has potential application value.

The object of the present invention is to provide a dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth compound.

Another object of the present invention is to provide a method for synthesizing the above-mentioned dihydrocarbylmethylene bridged fluorenylcyclopentadienyl rare earth complex.

The object of the present invention is also to provide a use of the above-mentioned dihydrocarbylmethylene bridged fluorenylcyclopentadienyl rare earth complex.

The dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex of the present invention has {[(X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )]MX ² (L) _n } _m molecular formula, wherein R ¹ , R ³ or R ⁴ =H or CH ₃ , R ² =H or C _1-4 alkyl, R ⁵ or R ⁶ = H, C _1-4 alkyl or Si(CH ₃ ) ₃ , R ⁷ =Si, C, Ge or Sn, X ¹ =C _1-4 alkyl or phenyl, X ² =Cl, BH ₄ , H, C _1-4 alkyl, H[(CH ₃ ) ₃ Si] ₂ , CH[(CH ₃ ) ₃ Si] ₂ , CH ₂ [(CH ₃ ) ₃ Si] or tetrahydrofuran (THF) group, M = Lanthanides, yttrium or scandium, L = (CH ₃ ) ₃ Si, Li(THF) ₄ , [Y-crown] or [Y-crown]-2,4-epoxyhexacyclo, n=1 Or 0, m=1 or 2, when m=2, n=0, Y=monovalent metal, crown ether=18-crown-6 or 15-crown-5. Or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are H, R ⁷ is C, X ¹ is phenyl, X ² is Cl, M=lanthanide, yttrium or scandium, L= ClLi(THF) ₄ , n=1, m=1; or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are H, R ⁷ is C, X ¹ is phenyl, X ² is BH ₄ , M=lanthanide, yttrium or scandium, L=BH ₄ Li(THF) ₄ , n=1, m=1; or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ is H, R ⁷ is C, X ¹ is phenyl, X ² is THF _n , M=lanthanide, yttrium or scandium, n=0, m=1;

The complexes of the present invention can also be represented by the following structural formula:

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , X ² , L, n and m are as above. The dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex of the present invention can be

等，

wait,

Where Ph = phenyl, t-Bu = tert-butyl, E = CH or N, THF = tetrahydrofuran.

X-ray single crystal diffraction analysis of some of the simpler molecule dihydrocarbylmethylene bridged fluorenylcyclopentadienyl rare earth complexes confirmed their structures after recrystallization.

The complexes {[(CH ₃ ) ₂ Si(C ₅ H ₅ )(C ₁₃ H ₈ )][YCl]} ₂ and {[Ph ₂ Si(t-Bu-C ₅ H ₃ )(C ₁₃ H ₈ )][YCl]} ₂ was recrystallized in toluene at low temperature to obtain two single crystals of Cs and C ₁ symmetric silicon-bridged fluorenylcyclopentadiene complexes 1 and 5. The main crystallographic data are listed in Table 1, and the main bond lengths and bond angles are listed in Table 2. They have the common characteristics of metal-bridged dimers. The crystal structures are shown in Figures 1 and 2.

          Table 1 Crystallographic data of complexes 1 and 5

Complex 1 5

Molecular formula C ₅₄ H ₅₂ Si ₂ Cl ₂ Y ₂ C ₇₄ H ₆₆ Si ₂ Cl ₂ Y ₂

Molecular weight 1005.89 1260.22

Crystal Form Triclinic Monoclinic

Color Yellow Yellow

T(K) 293 293

a() 11.669(2) 25.996(4)

b() 11.947(3) 10.008(2)

c() 9.286(2) 24.261(3)

α(°) 100.91(2) -

β(°) 100.00(1) 96.27(1)

γ(°) 72.22(2) -

V(A ³ ) 1201.2(5) 6274(1)

Z 1 4

Space Group P-1 C2/c

D/g cm ^-3 1.390 1.334

Accuracy Factor 0.064 0.065

           Table 2 The main bond lengths and bond angles of complexes 1 and 5

Complex 1 5

Y-Y’ 3.797(8) 3.659(1)

Y-Cl 2.649(2) 2.633(2)

Y-Cl’ 2.638(2) 2.648(4)

Y-C(1) 2.601(6) 2.604(6)

Y-C(2) 2.580(8) 2.645(6)

Y-C(3) 2.599(8) 2.702(6)

Y-C(4) 2.623(7) 2.645(6)

Y-C(5) 2.635(5) 2.648(5)

Y-C(7) 2.681(6) 2.632(6)

Y-C(8) 2.699(6) 2.732(6)

Y-C(9) 2.651(6) 2.825(6)

Y-C(10) 2.599(6) 2.745(5)

Bond angle (°)

Y-Cl-Y” 91.82(6) 88.0(1)

Cl-Y-Cl’ 88.18(6) 102.4(3)

Y-C(3)-C(31) - 128.0(4)

Y-C(3)-H(3) 124.4(4) -

C(5)-Si-C(6) 118.1(2) 116.1(2)

C(19)-Si-C(25) - 106.9(3)

C(20)-Si-C(19) 107.9(4) -

The complex [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )LuCl ₂ ][Li(THF) ₄ ]7 was recrystallized in THF/n-hexane mixed solvent to obtain the diphenylmethylene bridge Red crystals of bifluorenylcyclopentadienyllutetium chloride. X-ray single crystal diffraction analysis proves that it is an ionic compound composed of ion pairs separated from each other. Its molecular structure is shown in Figure 3. The main crystallographic data and main bond lengths and bond angles are listed in Tables 3 and 4, respectively. Its anionic part adopts a tetrahedral-like bridged metallocene structure. Such rare earth complexes containing (Cp) ₂ LnX ₂ ^-anion structure are rarely reported in the literature. The distance between the metal and the carbon atom on the metallocene ring is basically similar to the metal-carbon bond distance in other rare earth metallocene compounds, and the metal-carbon bond closer to the bridge atom carbon is shorter than the far metal-carbon bond. In this type of structure, the bond length between the central metal and the chloride ion is generally short, while the bond angle between the corresponding metal and the two chlorine atoms is relatively large.

The cation moiety [Li(THF) ₄ ] ⁺ of complex 7 is the same as the cation in the ionic complex. Lithium atoms coordinate with four tetrahydrofuran to form a tetrahedral structure. The bond length of the lithium-oxygen bond is in the range of 1.907(9)-1.934(9)A.

Table 3 Crystallographic data of complex 7 Molecular Formula Molecular Weight Color Crystal Form Space Group A()B()c() C ₄₇ H ₅₄ Cl ₂ LiO ₄ Lu935.76 red triclinic P-1 (#2) 12.529 (5) 15.280 (3) 12.247 (3) α(°)β(°)γ(°)V(A ³ )F000D _calc g/cm ³ T(k)μ _(Mo-Kα) (cm-1) 99.06(2)100.53(2)76.02(2)2173(1)952.002931.43024.35

    Table 4 The main bond lengths (A) and bond angles (°) of complex 7

Bond length () Bond angle (°)

Lu-Cl(1) 2.496(2) Cl(1)-L7-Cl(2) 96.48(7)

Lu-Cl(2) 2.501(2) Cl(1)-Lu-C(13) 126.3(1)

Lu-C(1) 2.631(5) Cl(2)-Lu-C(13) 124.8(1)

Lu-C(6) 2.818(5) Cl(1)-Lu-C(15) 126.6(1)

Lu-C(7) 2.841(5) Cl(2)-Lu-C(15) 126.7(1)

Lu-C(12) 2.673(6) C(1)-C(13)-C(14) 126.4(4)

Lu-C(13) 2.570(6) C(12)-C(13)-C(14) 125.8(4)

Lu-C(15) 2.561(5) C(13)-C(14)-C(15) 101.7(4)

Lu-C(16) 2.567(5) C(14)-C(15)-C(16) 124.9(4)

Lu-C(17) 2.615(5) C(14)-C(15)-C(19) 124.3(4)

Lu-C(18) 2.626(5) C(20)-C(14)-C(26) 103.5(4)

Lu-C(19) 2.577(5)

Dihydrocarbylmethylene bridged fluorenylcyclopentadienyl borohydride (C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )La(BH ₄ ) ₂ Li(THF) ₄ 9 and (C ₁₃ H ₈ ) CPh ₂ (C ₅ H ₄ )Nd(BH ₄ ) ₂ Li(THF) ₄ 10 also belongs to the anionic structure. The anion part is composed of π-ligand, rare earth ion and two molecules of _BH4 ligand; the cation is also composed of four molecules of THF complexed with a lithium ion. It has two obvious structural features: large BM-B' angle and short MB bond, and has the same crystal structure as complex 10. The crystallographic data and bond lengths and angles of complex 10 are listed in Tables 5 and 6, respectively, and the molecular structure diagram is shown in Figure 4.

     Table 5 Crystallographic data of complexes 9 and 10

Complex 9 10

Molecular formula C ₄₇ H ₆₂ B ₂ LaO ₄ Li C ₄₇ H ₆₂ B ₂ NdO ₄ Li

Molecular weight 858.47 863.81

color red red

2θmax(°) 26.3 26.2

Crystal Form Triclinic Triclinic

Space Group P-1(#2) P-1(#2)

a() 12.422(3) 12.415(6)

b() 16.343(4) 16.245(5)

c() 12.337(4) 12.337(5)

α(°) 110.50(2) 110.43(3)

β(°) 103.16(2) 103.23(4)

γ(°) 76.16(2) 76.13(3)

V(A ³ ) 2249(1) 2234(1)

T(K) temperature 293 293

Z 2 2

For its anion part {(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Nd(BH ₄ ) ₂ } ^- , the central metal neodymium ion coordinates with the fluorene ring and the fluorene ring in the η ³ -mode, and is symmetrical Ground connects two BH ₄ ^- ions, and the whole anion part is negative one valency. The angle ∠B1-Nd-B2(99.3(2)°) formed by the central metal neodymium and two boron atoms; the bond length of the two Nd-B bonds is relatively short, which obviously has the characteristics of tridentate coordination. The BH ₄ ligand exists in the tridentate coordination mode in this complex.

       Table 6 The primary bond lengths (A) and bond angles (°) of complexes 9 and 10

Complex 9(La) 10(Nd)

Ln-B(1) 2.717(5) 2.642(7)

Ln-B(2) 2.713(5) 2.658(6)

Ln-H(23) 2.37(6) 2.53(4)

Ln-H(24) 2.43(4) 2.38(6)

Ln-H(25) 2.38(5) 2.38(4)

Ln-H(27) 2.52(5) 2.39(4)

Ln-H(28) 2.49(5) 2.45(5)

Ln-H(29) 2.40(4) 2.45(5)

Ln-C(1) 2.845(3) 2.793(4)

Ln-C(6) 3.001(3) 2.946(4)

Ln-C(7) 3.010(3) 2.954(4)

Ln-C(12) 2.861(3) 2.806(4)

Ln-C(13) 2.788(3) 2.725(4)

Ln-C(15) 2.763(3) 2.701(4)

Ln-C(16) 2.769(3) 2.699(4)

Ln-C(17) 2.828(4) 2.771(4)

Ln-C(18) 2.830(4) 2.767(4)

Ln-C(19) 2.769(3) 2.708(4)

B(1)-H(23) 0.98(6) 1.05(5)

B(1)-H(24) 1.07(5) 0.97(5)

B(1)-H(25) 1.14(5) 1.05(5)

B(1)-H(26) 1.16(4) 1.04(6)

B(2)-H(27) 1.03(5) 1.09(5)

B(2)-H(28) 0.98(5) 1.05(6)

B(2)-H(29) 1.13(4) 0.99(5)

B(2)-H(30) 1.06(5) 1.10(5)

B(1)-Ln-B(2) 99.5(2) 99.3(2)

C(1)-C(13)-C(14) 126.6(3) 126.8(3)

C(12)-C(13)-C(14) 125.6(3) 125.3(3)

C(13)-C(14)-C(15) 102.1(2) 102.4(3)

C(14)-C(15)-C(16) 125.9(3) 125.5(3)

C(14)-C(15)-C(19) 125.8(3) 125.9(4)

C(20)-C(14)-C(26) 102.7(2) 103.1(3)

The increasing distance of carbon atoms on the carbocycle from the bridging carbon is also related to the nonbonding interaction between the two large _BH4 ligands. The closer the bridgehead carbon is to the carbon on the ring, the shorter the distance to the metal.

The characteristic structure of diphenylmethylene-bridged fluorenylcyclopentadienyl rare earth borohydrides is the special coordination mode of the metal with the _BH4 ligand. The two _BH4 ligands bond to the central metal almost completely symmetrically. Each BH ₄ and the central metal ion connect the boron atom and the metal atom through the μ ₃ -type hydrogen atom bridge. Complexes 7, 9 and 10 are composed of two mutually independent yin and yang, all of which have typical η ³ -coordination characteristics.

Dianionic Diphenylmethylene Bridged Fluorenylcyclopentadienyl Rare Earth Borohydride [K(18-Crown Ether-6){(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Nd(Bh ₄ ) ₂ }] ₂ (C ₄ H ₈ O ₂ )11, the neutral electron-donating ligand is no longer tetrahydrofuran or diethyl ether, but macrocyclic 18-crown 6 ether and 1, 4-epoxyhexane. The dianion rare earth borohydride 11 is composed of three independent parts. The molecular structure of complex 11 is shown in Figure 5. The main crystallographic data and key long-bond angles are listed in Tables 7 and 8, respectively.

Complex 11 has an anionic macrogroup {(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )-Nd(BH ₄ ) ₂ } ^- , and is charged with two positively charged cationic macrogroups {[K( 18-crown-6)] ₂ [C ₄ H ₈ O ₂ ]} ²⁺ separated. [K(18-crown-6)] ⁺ is formed as a whole by linking two oxygen atoms of 1,4-oxoxane C ₄ H ₈ O ₂ with a potassium atom respectively. The structure of the anion part of complex 11 is similar to those of 9 and 10, but there are obvious differences between them due to the different overall structures of the complexes. Its anion part {(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )-Nd(BH ₄ ) ₂ } ^- the central metal neodymium also coordinates with the fluorene ring and the fluorene ring in the η ³ -mode, and Two BH ₄ ^-ions are connected symmetrically.

         Table 7 The main crystallographic data of complex 11

Molecular formula C ₄₇ H ₅₈ NdB ₂ KO ₇ b() 20.217(2)

Molecular weight 915.91 c() 14.106(1)

Crystal Form Monoclinic β(°) 92.60(1)

Space group P2 ₁ /a V(A ³ ) 4424.0(9)

a() 15.530(3) color red

The longer distance from the metal center to the fluorene ring is also caused by the large steric hindrance of the fluorenyl group, and the bond length between the metal and the carbon atom on the fluorene ring also increases from the bridging carbon. The closer the bridgehead carbon is to the carbon on the ring, the shorter the distance to the metal. The two _BH4 ligands are also symmetrically bonded to the central metal. Each BH ₄ and the central metal ion also connect the boron atom and the metal atom through the μ3-type hydrogen atom bridge. The two Nd-B bonds also obviously have the characteristics of tridentate coordination, and the bond angles formed by the two Nd-BH _t are also almost in a straight line. In complex 11, two potassium ions not only bond with six oxygen atoms on 18 crown 6, but also connect with an oxygen atom in a 1,4-dioxane molecule respectively, forming {[K( 18-crown-6)][C ₄ H ₈ O ₂ ][K(18-crown-6)]} ²⁺ structure, which makes the whole cationic part a whole. Since the two anionic groups are listed on both sides of the cationic group, the whole molecule is composed of three independent parts.

Table 8 The main bond lengths () and bond angles (°) of complex 11

K-O(1) 2.754(6) B(1)-H(23) 0.97 Nd-B(2) 2.623(7)

K-O(2) 2.805(6) B(1)-H(24) 1.20 Nd-B(23) 2.47

K-O(3) 2.740(5) B(1)-H(25) 1.20 Nd-B(24) 2.40

K-O(4) 2.696(5) B(1)-H(26) 1.15 Nd-B(25) 2.41

K-O(5) 2.881(5) B(2)-H(27) 1.07 Nd-B(27) 2.48

K-O(6) 2.757(6) B(2)-H(28) 1.22 Nd-B(28) 2.39

K-O(7) 2.78(1) B(2)-H(29) 1.03 Nd-B(29) 2.52

K-C(3) 3.403(7) B(2)-H(30) 1.07 Nd-C(1) 2.817(5)

K-C(4) 3.322(7) Nd-B(1) 2.641(8) Nd-C(6) 2.938(6)

Nd-C(7) 2.915(6) Nd-C(15) 2.701(5) Nd-C(19) 2.718(5)

Nd-C(12) 2.781(5) Nd-C(16) 2.691(5) Nd-C(18) 2.753(6)

Nd-C(13) 2.752(5) Nd-C(17) 2.741(6)

B(1)-Nd-B(2) 100.2(3) C(1)-C(13)-C(14) 126.7(5)

C(12)-C(13)-C(14) 126.0(5) C(14)-C(15)-C(16) 126.0(5)

C(13)-C(14)-C(15) 103.1(4) C(14)-C(15)-C(19) 125.0(5)

C(20)-C(14)-C(26) 102.3(4) Nd-B(1)-H(26) 177.1

Nd-B(2)-H(30) 171.5

The difference between the structure of rare earth borohydride 11 and 9 and 10 is mainly due to the completely different coordination environment around the metal potassium ion compared to the complexation of tetramolecular tetrahydrofuran. The macrocyclic crown ether 18 crown 6 complexes with potassium ions to form a planar structure, and the coordination space around the potassium ions is relatively large, which can further coordinate with the π-ligand to form a bond, making the complex more stable; while tetramolecular tetrahydrofuran The complexation with alkali metal ions is generally a tetrahedral structure, and the alkali metal ions are not allowed to coordinate with other ligands in space. Therefore, in the structures of complexes 9 and 10, the anions and cations are isolated from each other, and they are linked together by electrostatic attraction; but in complex 11, the anions and cations are not completely isolated, and the The existence of weak mutual bonding makes the three relatively independent parts of the molecule organically connected into a whole.

The complexes [(CH ₃ ) ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]-DyCH(TMS) ₂ 14, [(CH ₃ ) ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]ErCH(TMS) ₂ 15, [(CH ₃ ) ₂ Si(C ₅ H ₄ )-(C ₁₃ H ₈ )]DyN(TMS) ₂ 16, [(CH ₃ ) ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]ErN(TMS) ₂ 17 and [Ph ₂ C(C ₅ H ₄ )-(C ₁₃ H ₈ )LuN(TMS) ₂ ] 18 - The crystal analyzed by ray single crystal diffraction, and its crystal structure was determined, as shown in Figures 6, 7 and 8, no matter the above-mentioned alkyl compound or amine complex has no solvent complexing molecules. The main bond lengths and bond angles of compounds 14, 16 and 17 are listed in Tables 9, 10 and 11.

Table 9 Main bond lengths () and bond angles (°) of complex 14

Bond length

Dy-C(27) 2.364(9) Dy-Si(2) 3.148(3)

Dy-C(21) 2.756(10) Dy-C(1) 2.589(10)

Dy-C(2) 2.66(1) Dy-C(3) 2.69(1)

Dy-C(4) 2.619(10) Dy-C(5) 2.604(9)

Dy-C(6) 2.592(8) Dy-C(7) 2.662(8)

Dy-C(8) 2.816(8) Dy-C(9) 2.830(9)

Dy-C(10) 2.666(8) Si(2)-C(21) 1.898(10)

Si(2)-C(27) 1.818(9) Si(3)-C(27) 1.840(8)

Si(3)-C(26) 1.88(2)

bond angle

Dy-C(27)-H(37) 100.2(9) Dy-C(27)-Si(2) 96.8(5)

Dy-C(27)-Si(3) 129.8(5) C(5)-Si(1)-C(9) 99.8(4)

C(10)-Si(1)-C(20) 108.2(5) C(2)-Dy-C(27) 102.8(4)

C(3)-Dy-C(27) 93.7(3) Si(2)-C(27)-Si(3) 123.5(5)

Dimethyl bridged fluorenyl cyclopentadienyl rare earth alkyl complex 14 belongs to the typical Cp' ₂ MX rare earth complexes. Similar to the crystal structure of other organic rare earth metallocene complexes coordinated by [(CH(TMS) ₂ ], the coordination mode of the five-carbon atom ring on the fluorenyl group and the metal has changed, and the fluorene ring in complex 14 It has obvious η ³ -coordination characteristics with the central rare earth metal ion, while the cyclocene and rare earth metal ions are still a typical η ⁵ -mode, which is similar to the structure of the amino complex 16, and the smaller one in the alkyl complex 14 The included angle of the bridgehead makes the tension on the bridgehead of the silicon atom significantly enhanced, forcing the distance from the metal to the carbon atom on the π-ring to be significantly longer; the distance between the central metal ion and the α-C on the alkyl CH(TMS) ₂ is very short, It is currently known as the shortest type of terminal σ-rare earth carbon bond. This is related to the large coordination space of complex 14; in addition, this structural feature is related to the symmetry of the complex. Usually it can be passed between MCH The included angle of α-CH...Ln agostic interaction is judged. The included angle of ∠Dy-C27-H37 in complex 14 is 100.29°, and the Dy-H37 bond (2.71 ) and the C27-H37 bond (0.972 ) The bond length does not change, and it is speculated that there is no α-CH...Lnagostic interaction.

Table 10 Main bond lengths () and bond angles (°) of complexes 16 and 17

Complexes 16 17

Bond length ()

Ln-N 2.207(5) 2.194(4)

Ln-C(21) 3.569(8) 3.667(7)

Ln-C(26) 2.901(8) 2.834(5)

Ln-Si(1) 3.407(2) 3.382(2)

LnSi(2) 3.469(2) 3.504(2)

LnSi(3) 3.152(2) 3.106(2)

Si(3)-C(26) 1.899(7) 1.896(5)

Si(3)-N 1.701(6) 1.697(4)

Si(2)-C(21) 1.861(9) 1.868(7)

Si(2)-N 1.699(5) 1.705(4)

Ln-C(1) 2.630(7) 2.596(6)

Ln-C(2) 2.657(8) 2.652(6)

Ln-C(3) 2.657(7) 2.647(5)

Ln-C(4) 2.615(7) 2.599(5)

Ln-C(5) 2.633(7) 2.603(4)

Ln-C(6) 2.618(6) 2.604(5)

Ln-C(7) 2.712(6) 2.670(5)

Ln-C(8) 2.843(6) 2.815(5)

Ln-C(9) 2.829(7) 2.816(5)

Ln-C(10) 2.675(6) 2.685(5)

Bond angle (°)

Si(2)-N-Si(3) 128.3(3) 127.1(2)

Ln-N-Si(3) 106.8(2) 105.2(2)

Ln-N-Si(2) 124.8(3) 127.6(2)

C(5)-Si(1)-C(6) 99.7(3) 99.5(2)

C(19)-Si(1)-C(20) 107.8(4) 107.7(3)

N-Ln-C(2) 93.0(2) 90.9(2)

N-Ln-C(3) 98.7(2) 98.2(2)

The single crystal of complex 18 was cultivated in a tetrahydrofuran-n-hexane mixed solvent, and its molecular structure was determined by X-ray single crystal diffraction analysis. As shown in the figure, the main bond lengths and bond angles are listed in Table 4- 10 in.

Compared with the structure of the corresponding diphenylmethylene bridged fluorenylcyclopentadienyl rare earth chloride, the amine complex of such ligands is no longer an ionic structure, but a solvent-free complex neutral complexes. Therefore, there is also a slight difference in the form of bonding between the metal and the two π-ligands. The distance from the central rare earth metal Lu to the carbon atoms on the two π-ring ligands is obviously shorter than that of its chloride. The steric hindrance around the metal ion is relieved, and the bonding between the metal and the π-ring ligand is enhanced.

Table 11 Main bond lengths () and bond angles (°) of complex 18

Bond length ()

Lu-C(32) 2.74(1) Lu-C(7) 2.558(9)

Lu-N 2.167(8) Lu-C(8) 2.568(10)

Lu-Si(1) 3.020(3) Lu-C(13) 2.741(9)

Si(2)-N 1.722(9) Lu-C(15) 2.541(10)

Si(1)-N 1.687(10) Lu-C(16) 2.533(9)

Si(1)-C(32) 1.89(1) Lu-C(17) 2.59(1)

Si(2)-C(37) 1.87(2) Lu-C(18) 2.58(1)

Lu-C(1) 2.731(10) Lu-C(19) 2.588(9)

Lu-C(6) 2.621(9)

Bond angle (°)

Lu-N-Si(11) 102.5 C(20)-C(14)-C(26) 103.2(8)

Lu-N-Si(2) 131.9(5) C(17)-Lu-N 93.3(4)

Si(2)-N-Si(1) 125.6(5) C(18)-Lu-N 103.1(4)

C(7)-C(14)-C(15) 101.1(7)

The metal-nitrogen bond length (Lu-N=2.167(8) Å) in the carbon atom-bridged complex 18 is basically the same as that in the silicon-bridged complex.

The crystallographic data of complexes 14, 16, 17 and 18 are listed in Table 11.

     Table 12 Crystallographic data of complexes 14, 16, 17 and 18

Complex 14 16 17 18

Molecular formula C ₂₇ H ₃₇ Si ₃ Dy C ₁₆ H ₃₆ Si ₃ Ndy C ₂₆ H ₃₆ Si ₃ Ner C ₃₇ H ₄₀ Si ₂ Nlu

Molecular weight 608.35 609.33 614.09 729.87

Crystal Form Monoclinic Monoclinic Triclinic

Color Yellow Yellow Yellow Red

a() 13.759(2) 9.123(1) 9.097(4) 15.777(3)

b() 9.077(9) 11.843(9) 11.759(4) 17.147(6)

c() 45.18(1) 25.522(4) 25.664(5) 14.434(5)

α(°) - - - - - - 110.10(3)

β(°) 91.06(2) 93.47(1) 93.41(3) 93.46(2)

γ(°) - - - - - - 91.39(2)

V(A ³ ) 5642(1) 2752.4(6) 2740(1) 3656(1)

Z 8 4 4 4

Space group P2 ₁ /n P2 ₁ /n P2 ₁ /n P-1

D/g cm ^-3 1.432 1.470 1.488 1.326

Accuracy factor 0.052; 0.066 0.034; 0.053 0.030; 0.039 0.057; 0.073

For the dimethylsilyl-bridged rare earth complexes, whether it is the alkylate 14 or the amides 16 and 17, they all belong to the monoclinic crystal system, P2 ₁ /n space group; and the carbon-bridged rare earth amine Complex 18 belongs to the triclinic crystal system, space group P-1.

In the molecular structure diagrams of these complexes, whether it is an alkyl or an amine ligand, it can be observed that one of the trimethylsilyl substituents has a small angle with the central metal ion, and the β-Si-Me There is an obvious interaction between the bond and the central rare earth ion.

Table 12 to Table 15 list the bond length and bond angle data related to the β-Si-Me...Ln agostic interaction in complexes 14, 16, 17 and 18, and the results show that in these complexes mainly β-Si- The C bond interacts with the central metal, not γ-C-H.

Table 13 The bond lengths of chemical bonds related to the "agostic" interaction in complex 14 ()

Chemical bond Bond length () Chemical bond Bond length () Chemical bond Bond length ()

Dy-C ₂₇ 2.364(9) Dy-H ₂₁ 2.50 Si ₂ -C ₂₂ 1.87(1)

Dy-Si ₂ 3.148(3) C ₂₇ -H ₃₇ 0.972 Si ₂ -C ₂₃ 1.86(1)

Dy-C ₂₁ 2.756(10) C ₂₁ -H ₁₉ 0.966 Si ₂ -C ₂₇ 1.818(9)

Dy-H ₃₇ 2.71 C ₂₁ -H ₂₁ 0.965 Si ₃ -C ₂₇ 1.840(8)

Dy-H ₁₉ 2.50 C ₂₁ -H ₂₀ 0.950

Dy-H ₂₀ 3.68 Si ₂ -C ₂₁ 1.90(1)

Table 14 The bond lengths of chemical bonds related to the "agostic" interaction in complexes 16 and 17 ()

chemical bond 16 17 chemical bond 16 17

Ln-N 2.207(5) 2.194(4) Si ₂ -C ₂₁ 1.861(9) 1.868(7)

Ln-Si ₃ 3.152(2) 3.106(2) Si ₂ -C ₂₂ 1.878(10) 1.864(7)

Ln-C ₂₆ 2.901(8) 2.834(5) Si ₂ -C ₂₃ 1.862(8) 1.869(7)

Ln-H ₃₅ 2.72 2.60 C ₂₆ -H ₃₄ 0.99 0.953

Ln-H ₃₆ 2.71 2.61 C ₂₆ -H ₃₅ 0.94 0.947

Ln-H ₃₇ 3.88 3.78 C ₂₆ -H ₃₆ 0.96 0.950

Si ₃ -C ₂₆ 1.899(7) 1.896(5) N-Si ₂ 1.699(5) 1.705(4)

Si ₃ -C ₂₄ 1.850(8) 1.864(6) N-Si ₃ 1.701(6) 1.697(4)

Si ₃ -C ₂₅ 1.862(8) 1.862(7)

Table 15 The bond lengths of chemical bonds related to the "agostic" interaction in complex 18 ()

Chemical bond Bond length () Chemical bond Bond length () Chemical bond Bond length ()

Lu ₁ -N ₁ 2.167(8) N ₁ -Si ₁ 1.867(10) C ₃₂ -H ₂₃ 0.97

Lu ₁ -C ₂ 2.74(1) N ₁ -Si ₂ 1.722(9) C ₃₂ -H ₂₄ 0.96

Lu ₁ -H ₂₃ 2.50 Si ₂ -C ₃₅ 1.85(2) C ₃₂ -H ₂₅ 0.94

Lu ₁ -H ₂₄ 2.50 Si ₂ -H ₃₆ 1.86(2)

Lu ₁ -H ₂₅ 3.50 Si ₂ -C ₃₇ 1.87(2)

The X-ray single crystal diffraction analysis of complexes 14, 16 and 18 showed that both the amine complexes and the alkyl complexes were neutral. The central metal ion and two π-ligands present a common chelate structure. The coordination form of the fluorene ring and the central metal ion is characterized by η ⁵ -. In the solid state, they all have intramolecular ^β Si-Me...Ln agostic interactions that make the complexes more stable.

The dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complexes of the present invention can be synthesized respectively by the following methods:

A monovalent metal salt with molecular formula (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ and equimolar MCl ₃ or M( BH ₄ ) ₃ (THF) ₃ is reacted in tetrachlorofuran solvent at -78°C to room temperature for 1-50h to generate {[(X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ ) (C ₁₃ H ₆ R ⁵ R ⁶ )][MCl]} _n 、(X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ )M(μ ₂ -Cl) ₂ Li-(THF ) ₄ or a rare earth borohydride (X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ )-M(BH ₄ ) ₂ Li(THF) ₄ having a dicationic structure.

The molecular formula is (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ , M(BH ₄ ) ₃ (THF) ₃ , 18- When the molar ratio of crown ether-6 or 15-crown ether-5 is 1:1:1-100, react in an organic solvent at -78°C to room temperature for 1-5h without 2,4-dioxane , generating [Y18-crown ether-6 or 15-crown ether-5]{(X ¹ ) ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )-M(C ₁₃ H ₆ R ⁵ R ⁶ )M (BH ₄ ) ₂ }. When the reaction contains 2,4-dioxane, {(X ¹ ) ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )M(C ₁₃ H ₆ R ⁵ R ⁶ )M(BH ₄ ) ₂ } ₂ [C ₄ H ₈ O ₂ ], the recommended molar ratio of the latter reaction is 1:1:1-100:1-100. 2,4-Dioxane may also be a compound present among crown ethers.

Use molecular formula (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ and equimolar calcium diiodide or ytterbium at -78°C React at room temperature for 10-50h to generate (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )-Sm or Yb-(THF) _m .

In an organic solvent, MCl ₃ and equimolar YCH(TMS) ₂ or YN(TMS) ₂ react at -78°C to 60°C for 10-80h to generate (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )MCH(TMS) ₂ or (X ¹ ) ₂ (R ⁷ )-(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )MN(TMS) ₂ .

Mix X ¹ ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )M(μ ₂ -Cl) ₂ Y(THF) ₄ with equimolar M ¹ N(TMS ) ₂ react in an organic solvent at -78°C to room temperature for 20-50h to generate [X ¹ ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )-(C ₁₃ H ₆ R ⁵ R ⁶ )]MN (TMS) ₂ .

In the above reaction, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , X ² , L, n, m, THF and Y are as described above, TMS=trimethyl Silicon base.

The complex synthesized by the above method can be recrystallized in a solvent, especially suitable for recrystallization in a polar and non-grade mixed solvent. Recrystallization should be at low temperature as well.

The dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl alkene complex of the present invention can be used as a catalyst for polymerization reaction, and can catalyze the polymerization reaction of methyl methacrylate, catalyze the polymerization of acrylic grease and the like. For example, the polymerization of methyl methacrylate shows a higher initiation activity, reaching 60-100%, and can obtain medium to better syndiotactic polymethyl methacrylate (rr=55-83%). The polymerization reaction can be carried out in a wider temperature range, and the obtained polymer has a higher molecular weight (Mn>10 ⁵ ) and a narrower molecular weight distribution (MW/Mn=1.215). The polymerization of acrylonitrile can also be catalyzed at moderate conversions of 40-60%.

Description of drawings

Figure 1 is the crystal structure of complex {[(CH ₃ ) ₂ Si(C ₅ H ₅ )(C ₁₃ H ₈ )][YCl]} ₂ 1

Figure 2 is the crystal structure of complex {[Ph ₂ Si(t-Bu-C ₅ H ₃ )(C ₁₃ H ₈ )][YCl]} ₂ 5

Figure 3 is the crystal structure of the complex [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )]LuCl ₂ ][Li(THF) ₄ ]7

Figure 4 is the crystal structure of the anion [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )Nd]Nd(BH ₄ ) ₂ ] of complex 10

Figure 5 is the crystal of complex [K(18-crown-6){(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Nd(BH ₄ ) ₂ }] ₂ [C ₄ H ₈ O ₂ ]11 structure

Figure 6 is the crystal structure of the complex [(CH ₃ ) ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]DyCH(TMS) ₂ 14

Figure 7 is the crystal structure of the complex [(CH ₃ ) ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]DyN(TMS) ₂ 16

Figure 8 is the crystal structure of complex [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )]LuN(TMS) ₂ ]18

The dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl alkene compound of the invention can not only be used as a catalyst for polymerization reaction, but also has a simple and convenient synthesis method, and is expected to be applied in industry.

The following examples will help to further understand the present invention, but can not limit the content of the present invention.

Example 1

1. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienyl yttrium chloride {[Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )][YCl]} ₂ (1)

Dissolve 1.83g (6.3mmol) of dimethylsilyl bridged fluorenylcyclopentadienyl ligand in 100ml of ether, slowly add 7.7ml (1.65M) of n-butyllithium dropwise under ice water cooling n-hexane solution, the solution turned from yellow to red, and reacted at room temperature for 5 hours. Then slowly drop the obtained ether solution of the dilithium salt of the ligand into 20ml ether in which 1.24g (6.36mmol) of YCl ₃ was suspended which had been cooled to -78°C, and slowly warm up to room temperature and stir for two days. The precipitate was separated by centrifugation, and the supernatant was transferred. Dry the solvent in vacuum, extract the solid product with 50ml of toluene, transfer the extract, slowly concentrate the solvent to 20ml in vacuo, place it at -20°C to cool and precipitate 0.56g (21.4%) of yellow crystals, mp: >320°C . Elemental analysis: C ₅₄ H ₂₂ Si ₂ Cl ₂ Y ₂ (1): Calculated C, 61.84; H, 4.83. Found: C, 62.12; H, 4.92%. MS(EI) (70 eV 50-400°C ): m/z821 (5.54, [M] ⁺ ), 663 (3.64, [M-YCl ₂ ] ⁺ ), 497 (12.35, [M-YCl ₂ -C ₁₃ H ₉ ] ⁺ ), 409 (100, [ M/2] ⁺ ), 374 (40.25, [M/2-Cl] ⁺ ). ¹ H NMR (300MHz, C ₆ H ₆ -D ₆ ): δ=8.06 (3, 2H, Flu, J=8.4Hz ), 7.89 (d, 2H, Flu, J=8.5Hz), 7.30 (m, 4H, Flu), 6.18 (m, 2H, Cp), 5.80 (m, 2H, Cp), 0.52 (s, 6H, SiMe ₂ ).FT-Raman (cm ^-1 ): 3067(m), 1527(s), 1437(s), 1336(vs), 1209(s), 1004(m), 740(m), 660(m ), 521(w).

2. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienyl lutetium chloride {[Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )][LuCl]} ₂ (2)

The experimental procedure is the same as the preparation of complex 1. 1.28g (4.54mmol) of LuCl ₃ was reacted with an equimolar amount of the dilithium salt of the ligand to obtain 0.35g (15.6%) of yellow crystals, mp: 220-222°C. Elemental Analysis: C ₅₄ H ₂₂ Si ₂ Cl ₂ Lu ₂ (2): Calculated for C, 46.37; H, 3.48. Found: C, 46.19; H, 3.74% MS (EI) (70eV, 50-400°C) : m/z993 (16.71, [M] ⁺ ), 749 (2.21, [M-YCl ₂ ] ⁺ ), 583 (4.65, [M-YCl ₂ -C ₁₃ H ₉ ] ⁺ ), 496 (100, [m /2] ⁺ , 461 (32.66, [M/2-Cl] ⁺ ). ¹ H NMR (300MHz, C ₆ H ₆ -D ₆ ): δ=8.04 (d, 2H, Flu, J=8.3Hz), 7.89(d, 2H, Flu, J=8.6Hz), 7.27(m, 2H, Flu), 7.16(m, 2H, Flu), 6.06(t, 2H, Cp, J=2.6Hz), 5.67(t, 2H, Cp, J=2.6Hz), 0.54(s, 6H, SiMe ₂ ).FT-Raman(cm ^-1 ): 3069(m), 1520(s), 1438(s), 1337(vs), 1209 (s), 1170(m), 740(m), 660(m), 521(w), 419(m), 292(m).

3. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienyl erbium chloride {[Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )][ErCl]} ₂ (3)

The experimental procedure is the same as the preparation of complex 1. 1.47g (5.35mmol) ErCl ₃ was reacted with an equimolar amount of the dilithium salt of the ligand to obtain 0.5g (19.2%) of yellow crystals, mp: >320°C. Elemental analysis: C ₅₄ H ₂₂ Si ₂ Cl ₂ Er ₂ (3): Calcd. C, 52.26; H, 4.11. Found: C, 52.35; H, 4.22%. MS (EI) (70eV, 50-400°C ): m/z981 (14.17, [M] ⁺ ), 947 (3.88, [M-Cl] ⁺ ), 743 (8.31, [M-YCl ₂ ] ⁺ , 575 (18.56, [M-YCl ₂ -Cl ₃ H ₉ ] ⁺ ), 489 (81.06, M/2) ⁺ ), 453 (100, [M/2-Cl] ⁺ ), FT-Raman (cm ^-1 ): 3067(m), 1527(s), 1438(s), 1338(vs), 1322(s), 1209(s), 1167(m), 1006(m), 740(m), 600(m), 521(w), 420(m), 290(m).

4. Preparation of Dimethylsilyl Bridged Fluorenylcyclopentadienyl Dysprosium Chloride {[Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )][DyCl]} ₂ (4)

The experimental procedure is the same as the preparation of complex 1. 1.11 g (4.13 mmol) of DyCl ₃ were reacted with an equimolar amount of the dilithium salt of the ligand to obtain 0.30 g (14.8%) of yellow crystals, mp: 240-244°C. Elemental analysis: C ₅₄ H ₂₂ Si ₂ Cl ₂ Dy ₂ (4): Calculated C, 53.08; H, 4.816. Found: C, 54.50; H, 4.27%. MS (EI) (70eV, 50-400°C ): m/z970 (1.00, [M] ⁺ ), 4.85 (2.35, [M/2] ⁺ ), 4450 (2.21, [M/2-Cl] ⁺ ).

Example 2

1. Preparation of diphenylsilyl-bridged fluorenylcyclopentadienyl yttrium chloride {[Ph ₂ Si(t-BuC ₅ H ₃ )(C ₁₃ H ₈ )][YCl]} ₂ (5)

Dissolve 4.36g (9.36mmol) of diphenylsilyl bridged fluorenyl tert-butyl substituted cyclopentadienyl ligand in 150ml of ether, slowly add 11.7ml (1.6M) of n-Butyl lithium in n-hexane solution, the solution changed from yellow to orange, reacted at room temperature for 5 hours. Then slowly drop the obtained ether solution of the dilithium salt of the ligand into the 10ml ether solution which had been cooled to -78°C and suspend 1.10g (5.64mmol) of YCl ₃ , and slowly raise the temperature to room temperature and stir the reaction for two days. The precipitate was separated by centrifugation, and the supernatant was transferred. The solvent was dried in vacuo, the obtained solid product was extracted with 50ml of toluene, the extract was transferred, the solvent was slowly concentrated in vacuo to 20ml, and 1.23g (37.1%) of yellow crystals were precipitated by cooling at -20°C, mp: 315-316°C. Elemental analysis: Calcd. for C ₇₄ H ₆₆ Si ₂ Cl ₂ Y ₂ (5), C, 70.70; H, 5.34. Found: C, 70.34; H, 5.57%. MS(EI) (70eV, 50-400°C ): m/z 554 (0.32, [M/2-Cl] ⁺ ), 302 (100, [C ₁₃ H ₈ -CPh ₂ ] ⁺ ). ¹ H NMR (300MHz, C ₆ H ₆ -D ₆ ): δ =7.2-8.2(m, CH(Ar)), 5.6-6.3(m, CHCp), 1.37(s, CH( ^tBu )).FT-Raman(cm ^-1 ): 3046(m), 1587(s ), 1529(s), 1335(vs), 1210(s), 998(vs), 672(m), 523(w), 425(m), 252(m).

2. Diphenylsilyl bridged fluorenyl tert-butyl substituted cyclopentadienyl dysprosium chloride {Ph ₂ Si(t-BuC ₅ H ₃ )(C ₁₃ H ₈ )}[DyCl]} ₂ (6) preparation

The experimental procedure is the same as the preparation of complex 5. 1.00 g (3.72 mmol) of DyCl ₃ was reacted with an equimolar amount of the dilithium salt of the ligand to obtain 1.76 g (71.5%) of yellow crystals, dp: 170°C. Elemental analysis: C ₃₄ H ₃₀ SiCl ₂ Dy(6): Calculated value C, 59.56; H, 4.38. Found value: C, 59.66; H, 4.51%. MS (EI) (70eV , 50-400°C): m /z1099 (4.23, [M] ⁺ ), 665 (60.89, [M/2] ⁺ ), 630 (17.59, [M/2-Cl] ⁺ ), 614 (74.16, [M/2-Cl-Me] ⁺ ), 302(100, [C ₁₃ H ₈ -CPh ₂ ] ⁺ ).

Example 3

1. Diphenylmethylene bridged fluorenyl cyclopentadienyl lutetium chloride (C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Lu(μ ₂ -Cl) ₂ Li(THF) ₄ (7) preparation of

Under the protection of argon, 42ml (0.1M) ligand dilithium salt (C ₁₃ H ₈ ) CPh ₂ (C ₅ H ₄ ) Li ₂ tetrahydrofuran solution was slowly added dropwise to the suspension which had been cooled to -78°C There was 1.58g (5.6mmol) LuCl ₃ in 20ml tetrahydrofuran solution, and the reaction solution was slowly raised to room temperature for two days. Centrifuge to separate the precipitate, transfer the supernatant, concentrate in vacuo to 10ml, slowly add n-hexane solution dropwise to the reaction solution, let stand at -20°C for several days, and then precipitate 1.35g (62.8%) of yellow crystals, mp:>320 ℃. Elemental analysis: C ₃₁ H ₂₂ LuCl ₂ Li: Calculated for C, 57.50; H, 3.40; Found: C, 57.40; H, 5.43%. ¹ H NMR (300 MHz; THF-d ₆ , 25°C): δ= 8.04(d, 2H, J=9.2Hz), 8.01(d, 2H, J=8.2Hz), 7.90(d, 2H, J=7.6Hz), 7.10(t, 2H, J=8.6Hz), 7.09( m, 4H), 6.97(t, 2H, J=7.1Hz), 6.84(t, 2H, J=8.6Hz), 6.48(d, 2H, J=8.7Hz), 5.92(t, 2H, J=2.6 Hz), 5.82(t, 2H, J=2.6Hz), FT-Raman(cm ^-1 ): 3061(m), 2986(m), 2889(m), 1595(w), 1529(m), 1436 (m), 1343(s), 1327(vs), 1002(s), 667(w), 438(m), 286(m).

2. Diphenylmethylene bridged fluorenyl cyclopentadienyl yttrium chloride (C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Y(μ ₂ -Cl) ₂ Li(THF) ₄ (8) preparation of

The experimental procedure is the same as the preparation method of complex 7. 1.40 g (7.2 mmol) of YCl ₃ was reacted with an equimolar amount of ligand dilithium salt to obtain 0.94 g (41%) of yellow crystals. Elemental analysis: C ₄₇ H ₅₄ YCl ₂ LiO ₄ : calculated for C, 66.38; H, 6.36; found: C, 65.52; H, 6.33%. ¹ H NMR (300 MHz; THF-d ₆ , 25°C): δ =8.08(d, 2H, J=7.9Hz), 8.00(d, 2H, J=8.2Hz), 7.90(d, 2H, J=7.5Hz), 7.29(t, 2H, J=7.8Hz), 7.09 (m, 4H), 6.98(t, 2H, J=7.1Hz), 6.81(t, 2H, J=7.8Hz), 6.52(d, 2H, J=8.7Hz), 5.90(t, 2H, J= 2.6Hz), 5.81(t, 2H, J=2.6Hz).FT-Raman(cm ^-1 ): 3055(m), 2888(m), 2875(m), 1530(w), 1435(m), 1326(vs), 1003(s), 668(w), 438(w), 286(m).

Example 4

1. Preparation of diphenylmethylene bridged fluorenyl cyclopentadienyl lanthanum borohydride (C ₁₃ H ₈ ) CPh ₂ (C ₅ H ₄ ) LaLi(THF) ₄ (9)

Under the protection of argon, slowly add 37ml (0.05M) ligand dilithium salt (C ₁₃ H ₈ ) CPh ₂ (C ₅ H ₄ ) Li ₂ tetrahydrofuran solution into the suspension cooled to -78°C. 0.85g (1.85mmol) La(BH ₄ ) ₃ (thf) ₃ in 15ml tetrahydrofuran solution, the reaction solution was slowly raised to room temperature for 4 hours. The precipitate was separated by centrifugation, the supernatant liquid was transferred, concentrated in vacuo to 10 ml, and n-hexane solution was slowly added dropwise to the reaction solution, and 0.35 g (22.3%) of orange crystals were precipitated after standing overnight, mp: 144-145°C. Elemental analysis: C ₄₇ H ₆₂ B ₂ LaO ₄ Li: Calculated C, 65.70; H, 7.22%; Found: C, 64.77; H, 7.09%. MS(EI) (70eV, 50-400°C): m /z764(9.10, [M-LiBH ₄ -THF] ⁺ ), 165(100, [C ₁₃ H ₉ ] ⁺ ). ¹ H NMR (300MHz; THF-d ₆ , 25°C): δ=8.44(m, 2H), 8.30(d, 2H, J=7.8Hz), 7.95(d, 2H, J=8.0Hz), 7.32-7.15(m, 2H), 7.30(m, 2H), 7.10(t, 2H, J =7.2Hz), 6.98(t, 2H, J=7.2Hz), 6.74(t, 2H, J=2.6Hz), 6.31(t, 2H, J=2.6Hz), -0.7-0.7(b, 8H) .FT-Raman (cm ^-1 ): 3064(m), 3052(m), 2984(m), 2887(m), 2413(m), 2218(m), 1585(w), 1530(w), 1436(m), 1346(m), 1326(vs), 1004(s), 667(w), 437(m), 289(m).

2. Preparation of Diphenylmethylene Bridged Fluorenylcyclopentadienyl Neodymium Borohydride (C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Nd(THF) ₄ (10)

The experimental procedure is the same as the preparation method of complex 9. React 0.89g (1.92mmol) of Nd(BH ₄ ) ₃ (FHF) ₃ with an equimolar amount of ligand dilithium salt to obtain 0.79g (47.6%) of yellow-green crystals, mp: 135-137°C. Elemental analysis: C ₄₇ H ₆₂ B ₂ NdO ₄ Li: Calcd. C, 65.29; H, 7.18; Found: C, 63.77; H, 6.88%. MS (EI) (70eV, 50-400°C): m/ z770(12.03, [M-LiBH ₄ -THF] ⁺ ), 165(100, [C ₁₃ H ₉ ] ⁺ ).FT-Raman(cm ^-1 ): 3064(m), 3052(m), 2984(m ), 2887(m), 2421(m), 2221(m), 1586(w), 1530(w), 1436(m), 1347(m), 1328(vs), 1004(s), 688(w ), 437(m), 280(m).

Example 5

1. Diphenylmethylene bridged fluorenylcyclopentadienyl neodymium borohydride [k(18-crown-6){(C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Nd(BH ₄ ) ₂ }] ₂ [C ₄ H ₈ O ₂ ] (11)

Under the protection of argon, 37.0ml (0.05M) ligand dilithium salt (C ₁₃ H ₈ ) CPh ₂ (C ₅ H ₄ ) K ₂ , 1- 100mmol tetrahydrofuran solution was slowly added to the 15ml tetrahydrofuran solution that had been cooled to -78°C suspended with 0.85g (1.85mmol) Nd(BH ₄ ) ₃ (thf) ₃ and 1ml of 18-crown- 6. The reaction solution was slowly raised to room temperature for 4 hours. The precipitate was separated by centrifugation, the supernatant liquid was transferred, concentrated in vacuo to 10 ml, and n-hexane solution was slowly added dropwise to the reaction solution, and 0.35 g (20.7%) of orange-yellow crystals were precipitated at 202-204° C. after standing overnight. Elemental analysis: C ₄₅ H ₅₈ NdB ₂ KO ₇ : Calculated C, 59.24; H, 6.19; Found C, 59.39; H, 6.56%. MS (EI) (70eV, 50-400°C): m/z 770( 12.03, [M-KBH ₄ -THF] ⁺ ), 165 (100, [C ₁₃ H ₉ ] ⁺ ).

Example 6

1. Preparation of Diphenylmethylene Bridged Fluorenylcyclopentadienyl Divalent Samarium [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )]Sm(THF) _n (12)

Add 1.57 g (3.88 mmol) samarium diiodide to 106 ml (3.9 mmol) [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )]K ₂ tetrahydrofuran of the dipotassium salt of the ligand at -78°C The solution was slowly raised to room temperature for two days. The precipitate was separated by centrifugation, and the supernatant was transferred and concentrated slowly to 20ml, and a large amount of precipitate was produced after standing for several days. The precipitate was vacuum-dried to obtain 1.06 g (45.3%) of a brown powder. Elemental analysis: (n=1): Calculated C, 68.07; H, 4.86. Found: C, 67.45; H, 4.71%.

Example 7

1. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienylalkyldysprosium [Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]DyCH[TMS] ₂ (14) (one-pot synthesis Law)

Under the protection of argon, 150ml dilithium salt [Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]Li ₂ (0.038M, 5.30mmol) ether solution was slowly added dropwise to the already Cool to -78°C and suspend DyCl ₃ (1.42g, 5.30mmol) in 20ml of tetrahydrofuran or benzene, then slowly raise the reaction solution to room temperature for two days. The reaction liquid was sucked under vacuum, and 100 ml of toluene solvent was added to make it into a suspension. Then the toluene solution was cooled to -78°C, 1.03g (6.2mmol) LiCH(TMS) ₂ was added, reacted at room temperature for one day, then heated to 60°C for one day, the color of the solution changed significantly to orange, and the reaction proceeded. The precipitate was separated by centrifugation, the supernatant was transferred, and the precipitate was extracted with 50 ml of toluene, and the supernatant was combined. Concentrate slowly to 20ml under vacuum, place at -20°C overnight, 0.52g (12.6%) of red crystals precipitate out, mp: 244-245°C. Elemental analysis: C ₂₇ H ₃₇ Si ₃ Dy(14), calculated for C, 51.25; H, 5.91. Found: C, 47.90; H, 6.55%. MS (EI) (70eV, 50-400°C): m /z609 (1.29, [M] ⁺ ), 594 (7.51, M-Me) ⁺ ), 450 (100, [M-CH(TMS) ₂ ] ⁺ ), 145 (30.38, [CH(TMS) ₂ ] ⁺ ).FT-Raman (cm ^-1 ): 3047(s), 2899(vs), 1531(m), 1322(s), 1210(m), 742(m), 657(m), 577(m) , 520(w), 431(m), 378(m), 236(s).

2. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienyl erbium [Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]ErCH[TMS] ₂ (15) (one-pot synthesis Law)

The experimental procedure is the same as the preparation method of complex 14. After reacting 1.47g (5.35mmol) ErCl ₃ with an equimolar amount of the ligand dilithium salt, and then reacting with 1.03g (6.2mmol) LiCH (TMS) in toluene, 0.24mg (7.3%) of orange-red crystals were obtained. . Elemental analysis: C ₂₇ H ₃₇ Si ₃ Er(15): Calculated value C, 52.85; H, 6.04. Real value: C, 51.00; H, 6.21%. MS (EI) (70eV, 50-400°C): m/z613 (2.13, [M] ⁺ ), 598 (2.08, [M-Me] ⁺ ), 454 (100, [M-CH(TMS) ₂ ] ⁺ ), 145 (46.84, [CH(TMS) ₂ ] ⁺ ).FT-Raman(cm ^-1 ): 3048(m), 2896(m), 1530(s), 1324(vs), 1211(s), 742(m), 657(m), 578( m), 520(w), 431(m), 378(m), 239(s).

Example 8

1. Preparation of dimethylsilyl-bridged fluorenylcyclopentadienylaminodysprosium [Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]DyN[TMS] ₂ (16) (one-pot synthesis Law)

Under the protection of argon, 150ml of dilithium salt [Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]Li ₂ (0.038M, 5.69mmol) ether solution was slowly added dropwise to the After cooling to -78°C, DyCl ₃ (1.53 g, 5.69 mmol) was suspended in 20 ml of tetrahydrofuran, and then the reaction solution was slowly raised to room temperature for two days. The reaction liquid was sucked under vacuum, and 100 ml of toluene solvent was added to make it into a suspension. Then the toluene solution was cooled to -78°C, 1.05g (5.3mmol) KN(TMS) ₂ was added, reacted at room temperature for one day, then heated to 60°C for one day, the color of the solution changed to red obviously, and the reaction proceeded. The precipitate was separated by centrifugation, the supernatant was transferred, and the precipitate was extracted with 50 ml of toluene, and the supernatant was combined. Concentrate slowly to 20ml under vacuum, and place it at -20°C overnight, and 1.32g (39.3%) of red crystals are precipitated, mp: 114-120°C. Elemental analysis: C ₂₆ H ₃₆ Si ₃ NDy(16), calculated for C, 51.20; H, 5.91; N, 2.30. Found: C, 50.71; H, 6.05; N, 2.67%. MS (EI) (70eV , 50-400°C): m/z610 (100, [M] ⁺ ), 594 (47.90, [M-Me] ⁺ ), 450 (75.55,, [MN(TMS) ₂ ] ⁺ ), 146 (47.41, [N(TMS) ₂ ] ⁺ ).FT-Raman(cm ^-1 ): 3047(s), 2898(vs), 1526(m), 1322(m), 1009(m), 742(w), 655 (w), 610(w), 430(w), 377(m), 237(s).

2. Preparation of Dimethylsilyl-Bridged Fluorenylcyclopentadienyl Amino Erbium[Me ₂ Si(C ₅ H ₄ )(C ₁₃ H ₈ )]ErN[TMS] ₂ (17) (one-pot synthesis Law)

The experimental procedure is the same as the preparation method of complex 16. React 1.30g (4.76mmol) ErCl ₃ with an equimolar amount of ligand dilithium salt, and then react with 1.08g (5.4mmol) KN(TMS) ₂ in toluene to obtain 0.33g (11.5%) of yellow crystals . Mp: 226-228°C. Elemental analysis: C ₂₆ H ₃₆ Si ₃ Er(16): Calculated value C, 50.81; H, 5.86; N, 2.28. Real value: C, 50.68; H, 6.03; N, 2.51%.MS(EI)( 70eV, 50-400°C): m/z 615 (18.30, [M] ⁺ ), 599 (9.31, [M-Me] ⁺ ), 453 (6.98, [MN(TMS) ₂ ] ⁺ ), 146 (100 , [N(TMS) ₂ ] ⁺ ).FT-Raman(cm ^-1 ): 3040(m), 2899(m), 1527(s), 1324(vs), 1211(s), 743(m), 656(m), 614(m), 520(w), 410(m), 378(m), 240(s).

3. Preparation of diphenylmethylene bridged fluorenylcyclopentadienylamino lutetium [Ph ₂ C(C ₅ H ₄ )(C ₁₃ H ₈ )LuN(TMS) ₂ (18)

Suspend 0.77g (1.27mmol) (C ₁₃ H ₈ )CPh ₂ (C ₅ H ₄ )Lu(μ ₂ -Cl) ₂ Li(THF) ₄ in 50ml of toluene, cool to -78°C and add 0.23g (1.15 mmol) KN(TMS) ₂ , raised to room temperature and reacted for two days. The precipitate was separated by centrifugation, the supernatant was transferred, concentrated to 30ml, and placed at -20°C, 0.09g (12.6%) of orange-red crystals were precipitated, mp: 170°C. Elemental Analysis: C ₃₇ H ₄₀ Si ₂ NLu(18): Calculated for C, 60.91; H, 5.49; N, 1.92. Found: C, 62.64; H, 5.63; N, 2.09%.MS(EI) (70eV , 50-400°C): m/z730 (19.14, [M] ⁺ ), 654 (21.91, [M-Ph] ⁺ ), 146 (65.71, [N(TMS) ₂ ] ⁺ ).1H NMR (300 MHz ; C ₆ H ₆ -D ₆ , 25°C): δ=8.25 (d, 2H, J=8.2Hz, CH(Ar)), 8.14 (d, 2H, J=6.5Hz, CH(Ar)), 8.0 (d, 2H, J8.1Hz, CH(Ar)), 7.0-7.5(m, CH(Ar)), 6.11(m, 2H, CH(Cp)), 6.30(m, 2H, CH(Cp)) , 0.35(s, 3H, CH ₃ (Si)), -0.20(s, 15H, CH ₃ (Si)).FT-Raman(cm ^-1 )∷3056(m), 2898(m), 1528(m ), 1435(m), 1327(vs), 1003(s), 741(m), 667(m), 618(m), 522(w), 440(m), 285(m).

Experimental Example 8

The results of dihydrocarbylmethylene bridged fluorenylcyclopentadienyl rare earth complexes synthesized using the aforementioned reaction conditions and different substituted substrates are listed in Table 13.

Table 13

Complex R1 2 R3 R4 R5 R6 R7 X1 X2 M Yield %

19 H H H H H H H C Ph N(TMS) ₂ Lu 12.6

20 H CH ₃ CH ₃ H t-Bu t-Bu Ge Et CH ₃ Sm 27.4

21 CH ₃ H ₃ CH ₃ CH ₃ Si(CH ₃ ) ₃ Si(CH ₃ ) ₃ Sn CH ₃ i-Pr Sc 35.3

22 H H H H H H H Si CH ₃ CH ₂ (TMS) Lu 15.5

23 H H H H H H H Si CH ₃ H Yb 14.6

24 H H H H t-Bu t-Bu Si H CH ₂ (TMS) Lu 20.7

Example 9

Complex 19:

Elemental Analysis: Calculated for C, 60.91; H, 5.49; N, 1.92. Found: C, 62.64; H, 5.63; N, 2.09%. MS (EI) (70eV, 50-400°C): m/z 730 (19.14, [M] ⁺ ), 654 (21.91, [M-Ph] ⁺ ), 146 (65.71, [N(TMS)2] ⁺ ). ¹ H NMR (300MHz; C ₆ H ₆ D ₆ 25°C) : δ=8.25(d, 2H, J=8.2Hz, CH(Ar)), 8.14(d, 2H, J=6.5Hz, CH(Ar)), 8.0(d, 2H, J=8.1Hz, CH( Ar)), 7.0-7.5(m, CH(Ar)), 6.11(m, 2H, CH(Cp)), 6.30(m, 2H, CH(Cp)), 0.35(s, 3H, CH ₃ (Si )), -0.20(s, 15H, CH ₃ (Si)).

Complex 20:

Elemental analysis: Calculated value C, 50.00; H, 5.69. Found value: C, 50.68; H, 5.63%. MS (EI) (70eV, 50-400°C): m/z 792 (16.14, [M] ⁺ ), 777(24.61, [M-Me] ⁺ ).

Complex 21:

Elemental analysis: Calculated value C, 62.20; H, 7.70. Found value: C, 62.68; H, 7.93%. MS (EI) (70eV, 50-400°C): m/z636 (25.75, [M] ⁺ ), 593(47.58, [M-iPr] ⁺ ).

Complex 22:

Elemental analysis: Calculated for C, 56.39; H, 5.45. Found: C, 57.32; H, 6.04%. ¹ H NMR (300MHz; C ₆ H ₆ -D ₆ 25°C): δ 8.00 (d, 2H, Flu , J=8.3Hz), 7.82(d, 2H, Flu, J=8.6Hz), 7.30(m, 2H, Flu), 7.22(m, 2H, Flu), 6.24(t, 2H, Cp, J=2.6 Hz), 5.85(t, 2H, Cp, J=2.6Hz), 0.38(s, 6H, SiMe ₂ ).-0.02(s, 9H, SiMe ₃ ). MS(EI) (70eV, 50-400℃) : m/z532 (5.23, [M] ⁺ ), 345 (69.34, [M-CH ₂ (TMS)] ⁺ ).

Complex 23:

Elemental analysis: Calculated value C, 53.40; H, 4.03. Found value: C, 54.08; H, 4.73%. MS (EI) (70eV, 50-400°C): m/z 472 (0.48, [M] ⁺ ), 307(27.69, [M-Flu] ⁺ ).

Complex 24:

Elemental analysis: Calculated for C, 57.78; H, 6.44. Found: C, 57.64; H, 6.25%. ¹ H NMR (300 MHz; C ₆ H ₆ -D ₆ ): δ 8.12 (d, 2H, Flu, J =8.3Hz), 7.87(d, 2H, Flu, J=8.6Hz), 7.40(m, 2H, Flu), 6.46(t, 2H, Cp, J=2.6Hz), 5.90(t, 2H, Cp, J=2.6Hz), 1.82 (s, 1 8H, t-Bu).-0.02 (s, 9H, SiMe ₂ ).MS (EI) (70eV, 50-400°C): m/z 644 (2.36, [ M] ⁺ ), 571(100, [M-CH ₂ (TMS)] ⁺ ).

Claims (10)

1. A dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex {[(X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )]MX ² (L) _n } _m , Has the following structural formula: Wherein R ¹ , R ³ or R ⁴ ＝H or CH ₃ , R ² ＝H, R ⁵ or R ⁶ ＝H, C _1-4 alkyl or Si(CH ₃ ) ₃ , R ⁷ ＝Si, C, Ge or Sn, X ¹ =C _1-4 alkyl or phenyl, X ² =Cl, BH ₄ , H, C _1-4 alkyl, N[(CH ₃ ) ₃ Si] ₂ , CH[( CH ₃ ) ₃ Si] ₂ , CH ₂ [(CH ₃ ) ₃ Si] or THF, M=lanthanides, yttrium or scandium, L=(CH ₃ ) ₃ Si, Li(THF) ₄ , [Y-crown ether] or [Y-crown ether]-2,4 epoxy hexacyclic ring, n=1 or 0, m=1 or 2, when m=2, n=0, Y=monovalent metal, crown ether=18 -crown-6 or 15-crown-5, THF=tetrahydrofuran. Or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are H, R ⁷ is C, X ¹ is phenyl, X ² is Cl, M=lanthanide, yttrium or scandium, L= ClLi(THF) ₄ , n=1, m=1; Or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are H, R ⁷ is C, X ^{1 is phenyl, X 2 is} BH ₄ , M=lanthanides, yttrium or scandium, L =BH ₄ Li(THF) ₄ , n=1, m=1; Or: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are H, R ⁷ is C, X ¹ is phenyl, X ² is THF _n , M = lanthanide, yttrium or scandium, n = 0, m = 1; 2. a dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1 is characterized in that it has the following structural formula:

or

Wherein M is as described in claim 1, Ph=phenyl, t-Bu=tert-butyl. 3. a dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1 is characterized in that it has the following structural formula:

Wherein M is as described in claim 1, E=CH or N. 4. a dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1 is characterized in that it has the following structural formula: Wherein Ph diphenyl, M as described in claim 1. 5. A dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1, characterized in that it has the following structural formula: Wherein M and THF are as described in claim 1. 6. A dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1, characterized in that it has the following structural formula: M and L in the base are as claimed in claim 1. 7. A dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1, characterized in that it has the following structural formula: Wherein M and N are as described in claim 1. 8. a kind of synthetic method that has dihydrocarbyl methylene bridging fluorenyl cyclopentadienyl rare earth complex as claimed in claim 1, it is characterized in that having following method synthesis: (1) A monovalent metal salt with a molecular formula of (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ and equimolar MCl ₃ or M(BH ₄ ) ₃ (THF) ₃ is reacted in tetrahydrofuran solvent at -78°C to room temperature for 1-50h to generate {[(X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ ) (C ₁₃ H ₆ R ⁵ R ⁶ )][MCl]} _n 、(X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ )M(μ ₂ -Cl) ₂ Li-(THF ) ₄ or (X ¹ ) ₂ (R ² )(C ₅ R ¹ R ² R ³ R ⁴ )M(BH ₄ ) ₂ Li(THF) ₄ ; (2) The molecular formula is (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ , M(BH ₄ ) ₃ (THF) ₃ and When the molar ratio of 18-crown ether-6 or 15-crown ether-5 is 1:1:1-100, react in an organic solvent at -78°C to room temperature for 1-5h to generate [Y(18-crown ether-6 or 15-crown-5)] {(X ¹ ) ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )M(C ₁₃ H ₆ R ⁵ R ⁶ )M(BH ₄ ) ₂ }; (3) The molecular formula is (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ , M(BH ₄ ) ₃ (THF) ₃ , When the molar ratio of 18-crown ether-6 or 15-crown ether-5 and 2,4-dioxane is 1:1:1-100:1:100, react in an organic solvent at -78°C to room temperature 1-5h generates [Y(18-crown ether-6 or 15-crown ether-5)]{(X ¹ ) ₂ R ⁷ (C ₅ R ¹ R ² R ³ R ⁴ )M(C ₁₃ H ₆ R ⁵ R ⁶ )M(BH ₄ ) ₂ } ₂ [C ₄ H ₈ O ₂ ]; (4) The molecular formula is (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ and equimolar samarium diiodide or ytterbium in - React at 78°C to room temperature for 10-50h to generate (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )-Sm or Yb-(THF) _m ; (5) The molecular formula is (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )Y ₂ in organic solvent with MCl ₃ and equimolar YCH( TMS) ₂ or YN(TMS) ₂ , react at -78°C to 60°C for 10-80h to generate [(X ¹ ) ₂ (R ⁷ )-(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )]MCH(TMS) ₂ or [(X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )]MN-(TMS ) ₂ ; (6) Combine (X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )M(μ ₂ -Cl) ₂ Y(THF) ₄ with mole The YN-(TMS) ₂ is reacted in an organic solvent at -78°C to room temperature for 20-50h to generate [(X ¹ ) ₂ (R ⁷ )(C ₅ R ¹ R ² R ³ R ⁴ )(C ₁₃ H ₆ R ⁵ R ⁶ )] NM(TMS) ₂ . 9. A method for synthesizing the dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl alkene complex as claimed in claim 8, characterized in that the single crystal is obtained by solvent recrystallization. 10. A use of the dihydrocarbyl methylene bridged fluorenyl cyclopentadienyl alkene complex as claimed in claim 1, characterized in that it is a catalyst for polymerization.

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