CN1732178A - Asymmetric group 8 (VIII) metallocene compounds - Google Patents
Asymmetric group 8 (VIII) metallocene compounds Download PDFInfo
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Abstract
Asymmetric, disubstituted metallocene compounds have the general formula CpMCp' where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentdienyl or indenyl moiety that includes at least one substituent group D1; Cp' is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D1'. D1 is different from D1'. D1 is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=O) Ca1Hb1Xc1; or Ca2Hb2Xc2O Ca1Hb1Xc1, where X is a halogen atom or nitro group; a1 is an integer between 2 and 8; b1 is an integer between 0 and 2 (a1)+1-c1; c1 is an integer between 0 and 2 (a1) + 1 - b1; b1 + c1 is at least 1; a2 is an integer between 0 and 8; b2 is an integer between 0 and 2 (a2) + 1 - c2; and c2 is an integer between 0 and 2 (a2) + 1 - b2; and D1' is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=O) Ca1Hb1Xc1; or Ca2Hb2Xc2O Ca1Hb1Xc1, where X is a halogen atom or nitro group; a1 is an integer between 1 and 8; b1 is an integer between 0 and 2 (a1) +1 -c1; c1 is an integer between 0 and 2 (a1) +1 -b1; b1 + c1 is at least 1; a2 is an integer between 0 and 8; b2 is an integer between 0 and 2 (a2) + 1 - c2; and c2 is an integer between 0 and 2 (a2) + 1 - b2. The compounds can be employed as precursors in film deposition processes.
Description
Background of invention
The chemical vapor deposition (CVD) method is applied to for example form material membrane on wafer or other surface in substrate in semi-conductor manufacturing or the processing.In CVD, cvd precursor (also claiming the CVD compound) is decomposed to form the film with required composition by heat, chemistry, photochemistry or the method by excitation of plasma.For example the gaseous state cvd precursor can contact with being heated to the substrate that temperature is higher than the decomposition temperature of described precursor, to form metal or metal oxide film in substrate.
Contain ruthenium (Ru), ruthenium oxide (RuO
2) or the film of iron (Fe) have excellent conducting performance and very high work function and chemistry and thermostability, the tolerance interlayer chemical species diffusion and with multiple dielectric base material compatibility.For example Ru and RuO
2Film has been studied the membrane electrode material as semiconducter device such as DRAM (dynamic RAM) device.
Two (pentahapto cyclopentadienyls) close ruthenium (ruthenocene) and symmetrical diethyl and replace ruthenocene (1,1 '-diethyl ruthenocene) and be studied as utilizing the CVD technology to form the possible precursor of ruthenium-based film.These compounds are by several synthetic route preparations.
Be used to prepare a kind of known method of ruthenocene shown in Figure 1A, by RuCl
3XH
2O and cyclopentadiene react in the presence of Zn and generate ruthenocene, ZnCl
2And HCl.Figure 1B show a kind of similar approach preparation 1,1 of adopting the ethyl substituted-cyclopentadienyl '-the diethyl ruthenocene.Usually the productive rate of this method is about 70%.
Shown in Fig. 1 C, do not replace ruthenocene and can pass through cyclopentadiene yet, chlorine (cyclopentadienyl) two (triphenylphosphines) closes ruthenium (II) and sodium hydride (NaH) and reacts in benzene and prepare.Chlorine (cyclopentadienyl) two (triphenylphosphines) closes ruthenium (II) precursor and reacts in ethanol by ruthenium trichloride and triphenylphosphine and synthesize.
The method of the another kind of synthetic ruthenocene of having studied comprises that two (alkyl cyclopentadienyl) closes iron cpd and RuCl
3XH
2The reaction of the metal transfer of O, the result with low-yield generate 1,1 '-dialkyl group ruthenocene and iron trichloride (FeCl
3), and very difficult separating ferrum class material.
Shown in Figure 1A and 1B, two cyclopentadienyl rings of these synthetic methods one step additions, therefore be suitable for preparation and do not replace ruthenocene or symmetry and replace 1,1 '-the diethyl ruthenocene.
Single replace ruthenocene such as 1-ethyl ruthenocene be as 1,1 '-impurity in the diethyl ruthenocene building-up process and generating.It is by two (cyclopentadienyl) closed ruthenium that the another kind of single ruthenocene that replaces, the tertiary butyl (cyclopentadienyl) (cyclopentadienyl) close ruthenium, and the mixture heating up of aluminum chloride and Tripyrophosphoric acid is then with trimethyl carbinol reaction and distill subsequently and prepare.
Ruthenocene and 1,1 '-vapour pressure of diethyl ruthenocene all relatively low (under 100 ℃ less than 10 holders).Under the room temperature ruthenocene be solid and 1,1 '-the diethyl ruthenocene is a liquid.
The usually preferred stronger cvd precursor of volatility for example is liquid rather than solid precursor under the room temperature.But the ideal cvd precursor also is thermolysis and can generates uniform film under suitable CVD condition in addition.
Therefore need under the exploitation room temperature for liquid and have the novel ruthenocene of higher vapor pressure and study their as the potentiality that are used for the sedimentary cvd precursor of film.Also need to develop other 8 family (VIII) Metallocenic compound that can be used as the cvd precursor that generates osmium or iron-based film.
Summary of the invention
The present invention relates generally to asymmetric 8 families (VIII) metallocenes.More specifically, the present invention relates to the compound of general formula CpMCp ', wherein M is the metal that is selected from Ru, Os and Fe; Cp is first substituted cyclopentadienyl or indenyl part, and this part comprises at least one substituent group D
1Cp ' is second substituted cyclopentadienyl or indenyl part, and this part comprises at least one substituent group D
1'.
D
1And D
1' two groups differ from one another and independent the selection.
D
1Can be:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1Perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is halogen atom or nitro (NO
2);
A1 is 2 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
D
1' can be:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1Perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is halogen atom or NO
2
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
A specific examples of Metallocenic compound of the present invention be the 1-methyl isophthalic acid '-the ethyl ruthenocene.
At least one can comprise one or more other substituting groups among Cp or the Cp ', as D
2, D
3, D
4, D
5, D
2', D
3', D
4' and D
5'.
The present invention has several advantages.The compounds of this invention provides extra selection and handiness for the existing method that is equipped with Ru-, Os-or Fe-base film by the CVD legal system.Some this compounds at room temperature is a liquid.Find in addition the 1-methyl isophthalic acid '-vapour pressure of ethyl ruthenocene is higher than 1,1 '-the diethyl ruthenocene.The standalone featureization of each cyclopentadienyl rings has changed many character such as solubleness, vapour pressure, decomposability, incendivity and other response path, reducing/oxidizing electromotive force, geometric configuration, preferred orientation and electron density distribution by the modification of cyclopentadienyl rings in the The compounds of this invention.The functionalization permission of cyclopentadienyl rings is made amendment to metallocenes or is optimized to be fit to required application.
The accompanying drawing summary
Figure 1A describes the synthetic route that a preparation does not replace the prior art of ruthenocene.
Figure 1B describe a preparation 1,1 '-synthetic route of the prior art of diethyl ruthenocene.
Fig. 1 C describes the synthetic method that another kind of preparation does not replace the prior art of ruthenocene.
Fig. 2 A shows the metallocenes molecular formula of staggered conformation.
Fig. 2 B shows the metallocenes molecular formula of opposed conformation.
Fig. 3 shows that the present invention two replaces the structural formula of asymmetric Metallocenic compound.
Fig. 4 shows the universal architecture formula of Metallocenic compound of the present invention.
Fig. 5 shows the asymmetric ruthenocene compound of exemplary the present invention.
Fig. 6 shows a kind of synthetic method that can be used for preparing Metallocenic compound of the present invention.
Fig. 7 show a kind of 1-of preparation methyl isophthalic acid '-synthetic method of ethyl ruthenocene.
Detailed Description Of The Invention
Above-mentioned and other target of the present invention, feature and advantage will clearly be manifested in to the more detailed description of the preferred embodiment of the invention (as shown in drawings) following, and identical part adopts same Reference numeral in different accompanying drawings.
Accompanying drawing not necessarily proportionally focuses on setting forth principle of the present invention.
The present invention relates generally to the asymmetric metallocene of 8 families (VIII). This place uses term " metallocene " to refer to Organometallic complexes, has the sandwich type structure of similar ferrocene, thinks that wherein transition metal and loop section close (electronics moves) with the π bond in the track that extends the ring above and below. In the described asymmetric metallocene, ring portion is divided into cyclopentadienyl group or indenyl herein. If 5 carbon atoms of all on the cyclopentadiene ring all with transition metal Cheng Jian, then cyclopentadienyl group or indenyl (cyclopentadienyl group and a phenyl ring condense) part also can be described as η5-coordination part. Therefore the complete description of ferrocene should be (η5-C
5H
5)
2Fe。
It is luxuriant that Fig. 2 A is depicted as the not substituted metal of staggered conformation, and wherein M is 8 families (VIII) metals, for example ruthenium, osmium or iron. Metallocene also can have the eclipsed conformation shown in Fig. 2 B. Molecular formula used herein is not to describe the concrete conformation of metallocene.
The present invention relates to the asymmetric metallocene of 8 families (VIII) of general formula CpMCp ', wherein M is Ru, Os or Fe. Cyclopentadienyl group and indenyl part are abbreviated as Cp herein. In an example, Cp and Cp ' are the cyclopentadiene base section. In another example, Cp and Cp ' are the indenyl part. In another example, one of Cp and Cp ' are cyclopentadienyl group, and another is indenyl.
At least one hydrogen (H) atom is substituted base such as D in each Cp of the compounds of this invention and the Cp ' part1And D1' replace.
D
1And D1' two groups differ from one another and independent the selection.
D
1Can for:
X；
C
a1H
b1X
c1；
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1 Perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is halogen atom, such as fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), perhaps NO2；
A1 is 2 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
D
1' can for:
X；
C
a1H
b1X
c1；
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1 Perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is halogen atom, for example F, Cl, Br or I, perhaps NO2；
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
The codomain of integer used herein comprises the border.
Can use straight chain and substitution in side chain base D
1And D
1'.D for example
1And/or D
1' can be straight chain or side chain C1-C8 alkyl.
In one embodiment of the invention, D
1Be selected from:
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1Perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is a halogen atom, as F, Cl, Br or I;
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is equal to, or greater than 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
B2+c2 is equal to, or greater than 1;
And D
1' be selected from:
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1, perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is a halogen atom, for example F, Cl, Br or I;
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1
C1 is the integer of 0 to 2 (a1)+1-b1
B1+c1 is equal to, or greater than 1
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2
C2 is the integer of 0 to 2 (a2)+1-b2
B2+c2 is equal to, or greater than 1.
In another embodiment, D
1Be halogen atom X, for example F, Cl, Br, I or NO
2And D
1' be selected from:
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1, perhaps
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is a halogen atom, for example F, Cl, Br or I, perhaps NO
2
A1 is 2 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1
C1 is the integer of 0 to 2 (a1)+1-b1
B1+c1 is equal to, or greater than 1
A2 is 0 to 8 integer
B2 is the integer of 0 to 2 (a2)+1-c2
C2 is the integer of 0 to 2 (a2)+1-b2
B2+c2 is equal to, or greater than 1.
Figure 3 shows that an example of Metallocenic compound of the present invention (CpMCp ') structural formula.
One of the Cp of Metallocenic compound of the present invention and Cp ' part or both also comprise one or more optional other substituent group D
xIn an example, at least one is polysubstituted cyclopentadiene base or indenyl part among Cp and the Cp '.
Figure 4 shows that the universal architecture formula of Metallocenic compound CpMCp ' of the present invention.D
1And D
1' independent as mentioned above the selection.D
2, D
3, D
4, D
5, D
2', D
3', D
4' and D
5' independently be selected from:
X，
C
a1H
b1X
c1；
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1；
C
a2H
b2X
c2OC
a1H
b1X
c1，
C
A2H
B2X
C2(C=O) OC
A1H
B1X
C1, perhaps
C
a2H
b2X
c2O(C＝O)C
a1H
b1X
c1
Wherein,
X is a halogen atom, for example F, Cl, Br, I, perhaps NO
2
A1 is 0 to 8 integer
B1 is the integer of 0 to 2 (a1)+1-c1
C1 is the integer of 0 to 2 (a1)+1-b1
B1+c1 is equal to, or greater than 1
A2 is 0 to 8 integer
B2 is the integer of 0 to 2 (a2)+1-c2
C2 is the integer of 0 to 2 (a2)+1-b2
B2+c2 is equal to, or greater than 1
The specific examples of ruthenium Base Metal cyclopentadinyl compound of the present invention sees Table 1 and Fig. 5.
Table 1
| The 1-methyl, 1 '-the ethyl ruthenocene | 1, the 2-dimethyl, 1 '-the ethyl ruthenocene |
| The 1-methyl, 1 '-the propyl group ruthenocene | The 1-methyl, 1 ', 3-diethyl ruthenocene |
| The 1-methyl, 1 '-the sec.-propyl ruthenocene | The 1-methyl, 1 ', 2-diethyl ruthenocene |
| The 1-methyl, 1 '-the butyl ruthenocene | The 1-methyl, 1 '-ethyl, 3-propyl group ruthenocene |
| The 1-methyl, 1 '-the sec-butyl ruthenocene | The 1-methyl, 1 '-propyl group, 3-ethyl ruthenocene |
| The 1-methyl, 1 '-tertiary butyl ruthenocene | The 1-ethyl, 1 '-methyl, 3-propyl group ruthenocene |
| The 1-ethyl, 1 '-the propyl group ruthenocene | The 1-methyl, 1 '-ethyl, 2-propyl group ruthenocene |
| The 1-ethyl, 1 '-the sec.-propyl ruthenocene | The 1-methyl, 1 '-propyl group, 2-ethyl ruthenocene |
| The 1-ethyl, 1 '-the butyl ruthenocene | The 1-ethyl, 1 '-methyl, 2-propyl group ruthenocene |
| The 1-ethyl, 1 '-the sec-butyl ruthenocene | The 1-methyl, 1 '-the propyl group ruthenocene |
| The 1-ethyl, 1 '-tertiary butyl ruthenocene | The 1-methyl, 1 '-the ethyl ruthenocene |
| The 1-propyl group, 1 '-the sec.-propyl ruthenocene | 1, the 3-dimethyl, 1 '-the ethyl ruthenocene |
| The 1-propyl group, 1 '-the butyl ruthenocene | 1,2,1 '-dimethyl, 3 '-the ethyl ruthenocene |
| The 1-propyl group, 1 '-the sec-butyl ruthenocene | The 1-butyl, 1 '-the ethanoyl ruthenocene |
| The 1-propyl group, 1 '-tertiary butyl ruthenocene | The 1-ethyl, 1 '-the methoxyl group ruthenocene |
| The 1-sec.-propyl, 1 '-the butyl ruthenocene | The 1-ethyl, 1 '-methoxyl group-2-oxyethyl group ruthenocene |
| The 1-sec.-propyl, 1 '-the sec-butyl ruthenocene | 1,2,3, the 4-tetramethyl-, 1 '-the ethyl ruthenocene |
| The 1-sec.-propyl, 1 '-tertiary butyl ruthenocene | The 1-ethanoyl, 1 '-the oxyethyl group ruthenocene |
| The 1-butyl, 1 '-the sec-butyl ruthenocene | The 1-difluoromethyl, 1 '-the ethyl ruthenocene |
| The 1-butyl, 1 '-tertiary butyl ruthenocene | The 1-trifluoromethyl, 2,3,4-fluoro-1 '-the trifluoromethyl ruthenocene |
| 1-sec-butyl ruthenocene, 1 '-tertiary butyl ruthenocene | The 1-vinyl, 1 '-the fluorine ruthenocene |
| 1,1 ', 3-trimethylammonium ruthenocene | The 1-ethoxyl methyl, 1 ', 2 '-the diethyl ruthenocene |
| 1,1 ', 2-trimethylammonium ruthenocene | The 1-ethyl, 1 '-the propoxy-ruthenocene |
| 1, the 3-dimethyl, 1 '-the ethyl ruthenocene | 1,1 ', 2,4-triethyl-3 '-the ethanoyl ruthenocene |
Metallocenic compound of the present invention also comprises the osmium base and the Fe-base compound of similar table 1 or compound shown in Figure 6.
In another U.S. Patent application of submitting to simultaneously with the application of David M.Thompson and Cynthia A.Hoover, announced the proper method of preparation Metallocenic compound of the present invention, the application name is called the method for preparing Metallocenic compound, act on behalf of case D-21245, this application is attached to herein by reference.
Described method comprises the bond salt compound, part (L) compound and a Cp compound (for example substituted-cyclopentadienyl (HCp)) generate midbody compound, gained midbody compound and second (Cp ') compound (compound that for example comprises cyclopentadienyl anion is as cyclopentadiene salt) reaction is generated the step of CpMCp '.
Metal-salt can be metal (III) salt, for example metal halide (such as muriate, bromide, iodide, fluorochemical), metal nitrate and other suitable metal-salt.M is 8 families (VIII) metals, for example Ru, Os or Fe.Usually metal-salt is abbreviated as MX
nThe MX that writes a Chinese character in simplified form used herein
nDo not repel the metal salt compound that contains combination water, the metal salt compound that contains combination water can more clearly be used formula as everyone knows in this area
Represent, wherein
Be not 0.So in specific examples, the FeX that writes a Chinese character in simplified form used herein
3Comprise molysite anhydrous and that contain combination water, these molysite can be used to prepare ferrocene or ferrocene compounds.
Part (L) is generally the electron pair donor(EPD) compound.Neutral electron pair donor(EPD) such as triphenylphosphine (PPh
3) be applied in one embodiment.Also can use tricyclohexyl phosphine and other general formula PR
3Phosphine and tris phosphite P (OR)
3, wherein R is a phenyl, cyclohexyl, alkyl or branched-chain alkyl such as the tertiary butyl.Other suitable electron pair donor(EPD) comprises amine, phosphoric acid ester, carbonyl compound, alkene, polyolefine, chelating phosphine, chelating amine and other compound.
The Cp compound is the precursor of the Cp part of above-mentioned CpMCp ' compound.Preferred Cp compound is HCp such as cyclopentadiene or indenes.The Cp compound also can be cyclopentadienyl or indenyl anion salt such as cyclopentadienyl potassium (KCp), cyclopentadienyl sodium (NaCp), cyclopentadienyl lithium (LiCp) etc.The suitable positively charged ion that uses with cyclopentadienyl anion in the synthetic method described herein comprises trimethylsilyl (TMS), Na, Li, K, Mg, Ca and Tl.
At least one hydrogen atom of Cp part is by D as mentioned above
1Group displacement.The specific examples of HCp comprises methyl cyclopentadiene, ethyl cyclopentadiene, n-propyl or sec.-propyl cyclopentadiene, normal-butyl, sec-butyl or tertiary butyl cyclopentadiene, halo cyclopentadiene etc.
The Cp compound also can be two replacements or polysubstituted, as is two, three, four and five substituted-cyclopentadienyls.Substituent group D
2, D
3, D
4And D
5Specific examples as mentioned above.
MX
n, L and HCp component all can respective pure form or optionally comprise suitable solvent version and provide.The used preferred solvent of method of the present invention comprises alcohol, as ethanol, and methyl alcohol, Virahol and other alcohol.Also can use ethyl acetate, tetrahydrofuran (THF) (THF), saturated or unsaturated hydrocarbons, aromatic heterocycle, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamine, nitrile, silicone oil and other aprotic solvent.Also can use combination solvent.
Common MX
n, L and Cp concentration selection be well known in the art.MX for example
nVolumetric molar concentration in suitable solvent can be about 0.1M to respective pure form.The volumetric molar concentration of L in suitable solvent can be about 0.1M to respective pure form.The volumetric molar concentration of Cp in suitable solvent can be about 0.1 to respective pure form.If use the phosphine of respective pure form then react with strong heat release.The method and the system of a large amount of reaction heat of dissipation per unit volume are well-known in this area.
Three components can any sequential combination.In one embodiment, metal component and HCp component join in the L component simultaneously.In another embodiment, metal component and HCp combination of components form mixture mixes mixture then with the L component, for example realizes by the L component is added in the mixture.In another embodiment, all components mixes simultaneously.
HCp and MX
nMol ratio be generally about 50 to about 1, preferred about 12 to about 2 and most preferably from about 7 to about 5.L and MX
nMol ratio be generally about 8 to about 0, preferred about 6 to about 2 and most preferably from about 5 to about 3.5.If use quite excessive HCp component, reaction will generate (Cp)
2The M product.
Temperature of reaction is preferably near the boiling point of employed solvent or the boiling point of reaction mixture.Other suitable temperature can be determined by normal experiment.Usually reaction can be carried out under near the temperature of boiling point being higher than the response composite zero pour.For example reaction can be about
To about
Between carry out.
Reaction times is depended on temperature and each concentration of reactants usually and can be for example about 5 minutes to about 96 hours.
Metal-salt (MX
n) intermediate component that generates of the reaction of component, part (L) component and HCp can use formula CpML
fX represents, wherein f=1 or 2.
In one embodiment by methods known in the art as filter, centrifugal or recrystallization separates as be solid CpML
fX.Make midbody compound CpML subsequently
fThe preferably reaction in the presence of solvent of X and Cp ' compound.Cp ' is preferably the negatively charged ion of the Cp ' part of the invention described above compound.Counter ion comprise trimethylsilyl (TMS), Na, Li, K, Mg, Ca and Tl.The specific examples of operable cyclopentadienyl compounds is including but not limited to ethyl cyclopentadiene sodium or lithium, methyl cyclopentadiene sodium or lithium, sec.-propyl cyclopentadiene sodium or lithium etc.Also can use two of Cp ' part to replace or polysubstituted negatively charged ion (as two, three, four or five substituted cyclopentadienyl negatively charged ion).Also can use as mentioned above not substituted indenyl negatively charged ion.
In a specific examples, midbody compound is CpRu (PPh
3)
2Cl.This compound and Cp ' reactant salt.Cp ' salt of recommending comprises NaCp ', LiCp ', (Cp ')
2Mg, TMS (Cp ') and (Cp ') Tl.
The example of suitable solvent comprises benzene,toluene,xylene, pentane, hexane, sherwood oil, fragrant heterocycle, saturated or unsaturated hydrocarbons, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamine, nitrile, polysiloxane etc.
Usually the volumetric molar concentration of Cp ' component in solvent arrives about 3.5M for about 0.1M, and preferably about 0.5M is to about 2.5M and most preferably from about 1.4 arrive 1.8M.
Cp ' and CpML
fThe mol ratio of X is generally about 50 to about 1, preferred about 6 to about 1 and most preferably from about 1.6 to about 1.2.
Separation of intermediates CpML not in another example
fThe X component.After forming midbody compound in the solution, Cp ' compound adds and contains CpML as mentioned above
fThe solution of X.
Cp ' and intermediate CpML
fBeing reflected at as mentioned above of X (no matter whether separating) carried out under the temperature and generated CpMCp ' product.
Reaction times is depended on temperature and each reactant concn usually, can be about 15 minutes to about 6 days.
Reaction product CpMCp ' can separate and/or purifying by methods known in the art, for example then distillation of solvent (as hexane) extraction, and distillation or chromatography or directly by distillation distil or chromatography is separated and/or purifying.
Also can use recrystallization, ultracentrifugation and other technology.Perhaps product can the reaction mixture form be further used and need not further be separated and/or purifying.
Chemical reaction shown in Figure 6 has been described a kind of method for preparing The compounds of this invention.In the described method of Fig. 6,
Triphenylphosphine and cyclopentadiene back flow reaction in ethanol generates midbody compound CpM (PPh
3)
2Cl, this midbody compound generate CpMCp ' with the reaction of ethyl cyclopentadiene sodium then.
One of Cp and/or Cp ' or the two can comprise other substituent group D x, for example group as mentioned above.One of Cp and/or Cp ' or the two can be two, three, four or five substituted-cyclopentadienyl parts.
Common asymmetric ruthenocene can be by at first producing intermediate CpRu (PPh
3)
2Cl is then with this intermediate and Cp ' reactant salt and prepare.Cp ' the salt of strong recommendation comprises NaCp ', LiCp ', (Cp ')
2Mg, TMS (Cp ') and (Cp ') Tl.If will synthesize CpRuCp ' type structure and when one of Cp or Cp ' comprise ketone, ester or ether functional group, preferably will contain greater amt ketone, the ring of ester or ether is defined as Cp ' ring, and it is joined intermediate as TMS salt.
Figure 7 shows that can be used for generating specific two replaces asymmetric ruthenocene such as 1-methyl, 1 '-synthetic schemes of ethyl ruthenocene or (methyl cyclopentadienyl) (ethyl cyclopentadienyl) ruthenium.As shown in Figure 7,
Triphenylphosphine and methyl cyclopentadiene back flow reaction in ethanol generates midbody compound chlorine (methyl cyclopentadienyl) two (triphenylphosphines) and closes ruthenium (II) or (η
5-C
5H
4C
2H
5) Ru (PPh
3)
2Cl, the reaction of this midbody compound and ethyl cyclopentadiene sodium generates the 1-methyl then, 1 '-the ethyl ruthenocene.
The technical examples that is used to characterize the compound that above-mentioned synthetic method generates includes but not limited to analyze gas-chromatography, nucleus magnetic resonance (NMR), thermo-gravimetric analysis (TGA), inductivity coupled plasma mass spectrometry (ICPMS), vapour pressure and viscosity measurement.
Do not explain the present invention although stick to specific mechanism, think the character such as specific function change such as solubleness, vapour pressure, decomposability, combustibility and other reaction path, reducing/oxidizing electromotive force, geometric configuration, preferred orientation and electron density distribution of each Cp and Cp ' ring.For example, think big more substituent group D
1And/or D
1' causing the increase of molecule entropy, this makes Metallocenic compound of the present invention compare with disclosed compound more to be tending towards at room temperature being in a liquid state.
Think that Metallocenic compound of the present invention can be used in the scientific research, for example can be used for ferrocene and ferrocene type molecule Organometallic Chemistry research and understand in and in the chemical reaction.
Think that The compounds of this invention also can be used as the combustion modifiers of solid propellant.In some cases, the functionalization of ferrocene parent can prevent that ferrocene from migrating into the insulating material on every side from solid propellant rubber-like adhesive substrate.
Metallocenic compound of the present invention can be used for katalysis, for example is used for the catalyzer of oxynitride reductive zeolite filler metal cyclopentadienyl catalyst or chirality organic synthesis.
Think that The compounds of this invention also can be used as vegeto-animal benefit chalybeate; Antioxidant and octane promoter; Motor spirit and oil additives; Coloured pigment; Radiation adsorber; And sterilant and mycocide.
The asymmetric metallocenes of the present invention is at preparation film, coating or powder, and is extremely useful as precursor in film depositing operation (as CVD technology) especially.This type of technology is seen and is set forth in David M.Thompson and Cynthia A.Hoover, the U.S. Patent application of submitting to simultaneously with the application of John Peck and Mike Litwin uses the deposition method of 8 families (VIII) metallocenes precursor, act on behalf of case number and be D-21267, this application is attached to herein by reference.
Embodiment
Embodiment 1
Steps A
5L five neck round-bottomed flasks are equipped with the mechanical stirring oar.Then with ethanol (2.0L) and PPh
3(420g 1.6mol) adds in this bottle.Two 500ml three-necked flask Teflon
Pipe (perfluorinated polymers, E.I.Du Pont Company) is connected to through volumetric pump on two mouths of these 5L four neck flasks, remaining mouthful prolong is installed.Heating jacket is placed in this 5L flask bottom, stirred solution and reflux.Triphenylphosphines all in backflow all are dissolved in the ethanol.When refluxing, nitrogen was fed system about 30 minutes.
Meanwhile, with RuCl
3XH
2O (100g, 0.40mol), ethanol (300mL) and a Teflon
The magnetic stir bar that (perfluorinated polymers, E.I.Du Pont Company) coats is inserted in the 500ml round-bottomed flask.Ethanolic soln is brown/orange immediately.Need heated solution so that RuCl
3XH
2O all dissolves.Utilize slotting wearing in plug and importing solution of needle tubing that is connected to source nitrogen, use purging with nitrogen gas solution 30 minutes, and wear every filling in to discharge unnecessary pressure with another root needle tubing is slotting, the metering gauge pressure of described source nitrogen is 1-2 pound/square inch (psig).
Preparation acetonitrile/the dry ice bath also immerses another 500ml flask wherein.Fresh distillatory methyl cyclopentadiene (190g, 270mL, 2.4mol, fresh distillation under nitrogen protection) is imported in the described refrigerative flask with conduit.
After the ethanolic soln of triphenylphosphine and ruthenium trichloride finished with purging with nitrogen gas, the content in two 500ml flasks pumped in the 5.0L flask by volumetric pump with speed independently respectively, and two are added on after 5 minutes and finish.For achieving this end, the ethyl cyclopentadiene is with the speed pumping of 45mL/min, and the ruthenium trichloride ethanolic soln is with the speed pumping of 50mL/min.
After interpolation finishes solution was refluxed 2 hours again.Can see that during this period tiny orange crystal is collected on the wall of solution meniscus top in the 2L flask.
Step B
Stir after 2 hours, with the volumetric pump on the 5L flask and
(perfluorinated polymers, E.I.Du Pont Company) pipe cuts off and connects.A distillation side arm is installed on the mouth of flask, removes about 1L ethanol by distillation.Stop mechanical stirring, orange crystallization is deposited to drag.In 3 hours with the solution cool to room temperature.Insert the Glass tubing that an end is connected to the coarse sintering head in flask, decompression makes solution shift out flask through the sintering head.Crystal washs with heptane (300ml), and removes heptane with similar method.Carry out three washings.
Step C
All openings of flask are all used rubber stopper seal, the flask and re-fill nitrogen three times of finding time.THF (500ml, anhydrous) is imported flask and starts mechanical stirring.(500mL, 1.2M 0.60mol) import in the 5L flask through conduit with the THF solution of ethyl cyclopentadiene lithium then.With these content reflux and stirred 4 hours.
Reflux after 4 hours, stop to stir, solution is changed in the 2L one neck round-bottomed flask.On Rotary Evaporators, solution concentration is about 200ml to volume.Then this heavy-gravity liquid is changed in the 250ml round-bottomed flask.
A short-path distillation head and a 100ml storage reception flask that has the Wei Geluo depression is installed on the described 250ml round-bottomed flask.Distillating liquid and obtain the 1-methyl under vacuum condition, 1 '-the ethyl ruthenocene, also contain the clarification yellow liquid of some triphenylphosphines (measuring) simultaneously with GCMS.Yellow liquid is revolved band distillation obtain the 1-methyl of 84.6g (productive rate 82%) purity greater than the no triphenylphosphine of 99% (GCMS, 1H NMR), 1 '-the ethyl ruthenocene, all the other impurity are 1,1 '-dimethyl ruthenocene and 1,1 '-the diethyl ruthenocene.TGA studies show that the Nonvolatile Residue of this liquid is less than 0.01%.
With a Teflon
(perfluorinated polymers, E.I.Du Pont Company) stirrer, ethanol (1.0L) and PPh
3(263g, 1.0mol, 5 equivalents) add in the 2L three neck round-bottomed flasks.With a 250ml dropping funnel, a 150ml dipping bath chuck dropping funnel and a prolong are installed on three mouths of 2L flask.Notice that two dropping funnels are equipped with Teflon
(perfluorinated polymers, E.I.Du Pont Company) valve so that in they and the round-bottomed flask environmental facies isolate.A rubber is equipped with every plug in 150ml dipping bath chuck dropping funnel top.Condenser overhead is equipped with a T joint and is connected to rare gas element.Place heating jacket, stirred solution and a reflux in 2L three neck round-bottomed flask bottoms.Triphenylphosphine all is dissolved in the ethanol in the backflow.System is used purging with nitrogen gas 3 hours during backflow.
Meanwhile, with RuCl
3XH
2O (50g, 0.20mol), ethanol (150mL, 1 equivalent) and a Teflon
The magnetic stir bar that (perfluorinated polymers, E.I.Du Pont Company) coats is inserted in the 500ml erlenmeyer flask.Ethanolic soln is brown/orange immediately.Need mild heat solution so that RuCl
3XH
2O all dissolves.With described solution impouring 250ml dropping funnel, a rubber is equipped with every plug in described dropping funnel top.Utilize slotting wearing in plug and importing solution of needle tubing that is connected to source nitrogen, use purging with nitrogen gas solution 30 minutes, and wear every filling in to discharge unnecessary pressure with another root needle tubing is slotting, the metering gauge pressure of described source nitrogen is 1-2 pound/square inch.
In 150ml dipping bath chuck dropping funnel, prepare methyl alcohol/the dry ice bath.The inner chamber of described dropping funnel adopts the method for similar other dropping funnel of purge to use purging with nitrogen gas 30 minutes.Then methyl cyclopentadiene (6 equivalents distill in nitrogen twice for 96.2g, 1.2mol) is imported in the refrigerative dropping funnel every plug by rubber.
2L round-bottomed flask purge after 3 hours, is completely cut off the Teflon of dropping funnel and system rest part
(perfluorinated polymers, E.I.Du Pont Company) valve is all opened, and beginning drips two kinds of solution simultaneously.Described two kinds of solution all are added dropwise to PPh after 20 minutes
3In the ethanolic soln.Solution is in reflux state during this period.It is tenne deeply that solution is rapidly.After dropwising, solution refluxed 2 hours again.Can see CpRu (PPh during this period
3)
2The tiny orange crystal of Cl is collected on the wall of solution meniscus top in the 2L flask.
Connect the pipeline that one one end is connected with rough porous sintering head on the volumetric pump.The sintering end of pipeline is immersed in the reactor, pump all liquid in the 2L round-bottomed flask.In this stage dropping funnel is removed from reactor.K head distillation joint is installed on a mouth, and another mouthful gone up and rubber is installed every plug.Flask is found time and re-fill nitrogen three times.Under nitrogen protection, dry toluene (1.0L) is imported in the 5L flask every plug by rubber.This dark opaque solution is heated to backflow, opens K head distillation joint to steam a part of solvent.Collect overhead product and reach 109 ℃ (noticing that in different experiments this will consume the solvent of different volumes-be generally 400-600ml liquid) until tip temperature.Then solution is cooled to below the reflux temperature.
Extra toluene is added in the flask to obtain the toluene of the about 600ml of volume.(35g, 0.35mol 400mL) import in the retort with the toluene slurry of ethyl cyclopentadiene lithium then.Finish, under 80 ℃ with solution stirring 4 hours.In this stage flask is shifted out glove box, and remove most of toluene with K head distillation joint.
In remaining liquid (about 400ml) impouring 1.0L round-bottomed flask.A short-path distillation head and a distillation that has the Wei Geluo depression is installed on described round-bottomed flask.The liquid of collecting from the Wei Geluo rectifying column obtains the 1-methyl of the clarifying yellow liquid shape of 44g with revolving the distillation once more under vacuum condition of band distillation method, 1 '-the ethyl ruthenocene, purity is greater than 99% (GCMS).TGA studies show that the contained Nonvolatile Residue of this liquid is less than 0.01%.
Embodiment 3
Prepare ethyl cyclopentadiene lithium as follows.With Teflon
(perfluorinated polymers, E.I.Du Pont Company) stirrer is put into 2L three neck chuck round-bottomed flasks.With a stopcock joint, a thermometer wrap tube stub and a rubber that has thermowell is installed on three mouths of described flask every plug.A nitrogen/vacuum manifold is connected on the stopcock joint, flask is found time to charge into nitrogen three times again.Then dry toluene (1.0L) is imported in the flask and starts every plug by rubber and stir.A cryogenic liquid circulator is put to the outer of chuck flask with the nalgene pipe coupling, at the outer wall circulation cryogenic liquid (15 ℃) of chuck flask.In case toluene reaches-10 ℃, (127g 1.35mol) imports in the flask with the ethyl cyclopentadiene of fresh distillation (distillatory middle runnings on a Wei Geluo rectifying column).(1.28mol), boot speed is lower than 0 ℃ with holding temperature and is as the criterion (importing about 2 hours) for 800mL, 1.6M hexane solution slowly to import n-Butyl Lithium in the middle of stirring.In the process that imports n-Butyl Lithium, in the solution tiny white precipitate (ethyl cyclopentadiene lithium) can appear.
This product can suspension uses or is solid by filtering and removing separated from solvent.
With THF (50mL, anhydrous, unrestraint agent), chlorine (ethyl cyclopentadiene) two (triphenylphosphines) closes ruthenium (II) (3.22g, 0.004mol, 1 equivalent) and Teflon
(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box.Stirred solution slowly adds the THF solution (0.20M, 30mL, 1.5 equivalents) of light violet magenta sec.-propyl cyclopentadiene sodium.Finish, solution is scarlet.Meniscus is yellow in 30 minutes.Solution stirring is spent the night.
Extracting sample aliquot (1.0ml) from solution analyzes with GC/MS.The peak that to observe a quality be 301g/mol and 1-ethyl-1 '-sec.-propyl ruthenocene consistent.Also observe other and alkyl cyclopentadiene dipolymer, 1,1 '-the diethyl ruthenocene, 1,1 '-peak of the uniform quality of di-isopropyl ruthenocene and triphenylphosphine.
Under reduced pressure from flask, remove the THF solvent then.Vacuum jacket short-path distillation joint is installed, (～0.1 holder) distillation that the content in the flask is reduced pressure on the 250ml flask.Collect light yellow liquid (0.72g).Then with this liquid of chromatography purification.Use the pentane solution of silica gel.Post directly is 0.75 ", column length is 6 ".Utilize the look popularize law separate 0.53g 99+% purity 1-ethyl-1 '-sec.-propyl ruthenocene (productive rate 41%).
Embodiment 5
With THF (50mL, anhydrous, unrestraint agent), chlorine (methyl cyclopentadiene) two (triphenylphosphines) closes ruthenium (II) (5.02g, 0.007mol, 1 equivalent) and Teflon
(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box.Stirred solution slowly adds the THF solution (0.20M, 50mL, 1.5 equivalents) of light violet magenta sec.-propyl cyclopentadiene sodium.Finish, solution is scarlet.Meniscus is yellow in 30 minutes.Solution stirring is spent the night.
Extracting sample aliquot (1.0ml) from solution analyzes with GC/MS.The peak that to observe a quality be 287g/mol and 1-methyl isophthalic acid '-sec.-propyl ruthenocene consistent.Also observe other and alkyl cyclopentadiene dipolymer, 1,1 '-the dimethyl ruthenocene, 1,1 '-peak of the uniform quality of di-isopropyl ruthenocene and triphenylphosphine.
Under reduced pressure from flask, remove the THF solvent then.The short neck distillation of vacuum jacket joint is installed, (～0.1 holder) distillation that the content in the flask is reduced pressure on the 250ml flask.Collect light yellow liquid (1.78g).Then with this liquid of chromatography purification.Use the pentane solution of silica gel.Post directly is 0.75 ", column length is 6 ".Utilize the look popularize law separate 1.03g 98+% purity the 1-methyl isophthalic acid '-sec.-propyl ruthenocene (productive rate 53%).
Embodiment 6
Two (propyl group cyclopentadiene) closed magnesium (5.15g, 0.02mol, 1 equivalent), and chlorine (methyl cyclopentadiene) two (triphenylphosphines) closes ruthenium (II) (5.02g, 0.007mol, 1 equivalent) and Teflon
(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box.Toluene (120ml, anhydrous, unrestraint agent) is imported the 250ml round-bottomed flask, stir content.Solvent finishes, and solution is scarlet.
Under reduced pressure from flask, remove toluene solvant then.Decompression removes toluene solvant, and on flask the short-path distillation joint is installed.Collect overhead product, GC/MS show the short-path distillation main fraction be 88.7% purity 1-propyl group-1 '-' the ethyl ruthenocene.
Be equal to statement
Although the present invention at length shows and be described with reference to its preferred embodiment, those skilled in the art can understand in not departing from the scope of the present invention that claims forgive, can make on the various forms and details on change.
Claims (10)
1. the asymmetric metallocenes of 8 families (VIII) of a general formula CpMCp ', in the described metallocenes:
M is the metal that is selected from Ru, Os and Fe;
Cp is the cyclopentadienyl or the indenyl part of first replacement, and this part comprises at least one substituent group D
1
Cp ' is the cyclopentadienyl or the indenyl part of second replacement, and this part comprises at least one substituent group D
1';
Wherein
D
1With D
1' difference;
D
1Be selected from:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1And
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is F, Cl, Br, I or NO
2
A1 is 2 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
And
D
1' be selected from:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1And
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is F, Cl, Br or I or NO
2
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is equal to, or greater than 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2; And
B2+c2 is equal to, or greater than 1.
2. the asymmetric metallocenes of claim 1, wherein one of Cp and Cp ' or both contain at least one other substituent group D x, and wherein said Dx is selected from:
X；
C
a1H
b1X
c1；
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1；
C
a2H
b2X
c2OC
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) OC
A1H
B1X
C1And
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1
Wherein
X is F, Cl, Br or I or NO
2
A1 is 0 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is equal to, or greater than 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2; And
B2+c2 is equal to, or greater than 1.
3. Metallocenic compound of representing by following molecular formula
Wherein:
M is selected from Ru, Os and Fe;
D
1Be different from D
1' and D
1And D
1' independently be selected from:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1And
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is F, Cl, Br, I or NO
2
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2; And
C2 is the integer of 0 to 2 (a2)+1-b2.
4. the Metallocenic compound of claim 3, wherein said D
1Be methyl and D
1' be selected from ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl and the tertiary butyl.
5. the Metallocenic compound of claim 3, wherein said D
1Be ethyl and D
1' be selected from propyl group, sec.-propyl, normal-butyl, sec-butyl and the tertiary butyl.
6. the Metallocenic compound of claim 3, wherein said D
1Be propyl group and D
1' be selected from sec.-propyl, normal-butyl, sec-butyl and the tertiary butyl.
7. the Metallocenic compound of claim 3, wherein said D
1Be sec.-propyl and D
1' be selected from normal-butyl, sec-butyl and the tertiary butyl.
8. the Metallocenic compound of claim 3, wherein said D
1Be normal-butyl and D
1' be selected from the sec-butyl and the tertiary butyl.
9. the Metallocenic compound of claim 3, wherein said D
1Be sec-butyl and D
1' be the tertiary butyl.
10. the compound of a following general formula
Wherein:
D
1And D
2Different and independently be selected from:
X；
C
a1H
b1X
c1；
C
A2H
B2X
C2(C=O) C
A1H
B1X
C1And
C
a2H
b2X
c2OC
a1H
b1X
c1，
Wherein
X is F, Cl, Br, I or NO
2
A1 is 1 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is at least 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2; And
D
2, D
3, D
4, D
5, D
2', D
3', D
4' and D
5' independently be selected from:
X；
C
a1H
b1X
c1；
C
a2H
b2X
c2(C＝O)C
a1H
b1X
c1；
C
a2H
b2X
c2OC
a1H
b1X
c1，
C
A2H
B2X
C2(C=O) OC
A1H
B1X
C1And
C
a2H
b2X
c2O(C＝O)C
a1H
b1X
c1，
Wherein
X is F, Cl, Br, I or NO
2
A1 is 0 to 8 integer;
B1 is the integer of 0 to 2 (a1)+1-c1;
C1 is the integer of 0 to 2 (a1)+1-b1;
B1+c1 is equal to, or greater than 1;
A2 is 0 to 8 integer;
B2 is the integer of 0 to 2 (a2)+1-c2;
C2 is the integer of 0 to 2 (a2)+1-b2;
B2+c2 is equal to, or greater than 1.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42294602P | 2002-10-31 | 2002-10-31 | |
| US60/422,946 | 2002-10-31 | ||
| US60/422,947 | 2002-10-31 | ||
| US60/426,284 | 2002-11-14 | ||
| US60/427,461 | 2002-11-18 | ||
| US60/446,320 | 2003-02-07 | ||
| US60/453,717 | 2003-04-18 | ||
| US60/453,719 | 2003-04-18 | ||
| US60/453,718 | 2003-04-18 | ||
| US10/685,785 | 2003-10-16 | ||
| US10/686,254 | 2003-10-16 | ||
| US10/685,777 | 2003-10-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1732178A true CN1732178A (en) | 2006-02-08 |
| CN100349912C CN100349912C (en) | 2007-11-21 |
Family
ID=35964228
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801079256A Expired - Fee Related CN100349911C (en) | 2002-10-31 | 2003-10-30 | Methods for making metallocene compounds |
| CNB2003801079260A Expired - Fee Related CN100349912C (en) | 2002-10-31 | 2003-10-30 | Asymmetric group 8 (VIII) metallocene compounds |
| CNB2003801078395A Expired - Fee Related CN100543178C (en) | 2002-10-31 | 2003-10-30 | Use the deposition method of 8 families (VIII) metallocenes precursor |
Family Applications Before (1)
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| CNB2003801079256A Expired - Fee Related CN100349911C (en) | 2002-10-31 | 2003-10-30 | Methods for making metallocene compounds |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2003801078395A Expired - Fee Related CN100543178C (en) | 2002-10-31 | 2003-10-30 | Use the deposition method of 8 families (VIII) metallocenes precursor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112204168A (en) * | 2018-06-13 | 2021-01-08 | 巴斯夫欧洲公司 | Method for producing a film comprising a metal or semimetal |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090205538A1 (en) * | 2008-01-24 | 2009-08-20 | Thompson David M | Organometallic compounds, processes for the preparation thereof and methods of use thereof |
| CN102776486A (en) * | 2012-08-07 | 2012-11-14 | 中国科学院半导体研究所 | Atomic layer deposition method of BiFeO3 film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294685A (en) * | 1952-04-21 | 1966-12-27 | Gulf Research Development Co | Organic compositions containing a metallo cyclopentadienyl |
| US3035978A (en) * | 1957-08-12 | 1962-05-22 | Ici Ltd | Ferrocene hematinic compositions and therapy |
| GB864198A (en) * | 1959-01-07 | 1961-03-29 | Ici Ltd | A process for the manufacture of ferrocene derivatives |
| US3535356A (en) * | 1968-06-11 | 1970-10-20 | Gulf Research Development Co | Process for producing dicyclopentadienyliron compounds |
-
2003
- 2003-10-30 CN CNB2003801079256A patent/CN100349911C/en not_active Expired - Fee Related
- 2003-10-30 CN CNB2003801079260A patent/CN100349912C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112204168A (en) * | 2018-06-13 | 2021-01-08 | 巴斯夫欧洲公司 | Method for producing a film comprising a metal or semimetal |
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|---|---|
| CN1732286A (en) | 2006-02-08 |
| CN100349912C (en) | 2007-11-21 |
| CN1732177A (en) | 2006-02-08 |
| CN100543178C (en) | 2009-09-23 |
| CN100349911C (en) | 2007-11-21 |
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