CN1990491B - Volatile metal beta-ketoiminate and metal beta-diiminate complexes - Google Patents

Abstract

Volatile metal beta-ketoiminate and metal beta-diiminate complexes are disclosed. The invention provides the metal ketoiminate complexes, and a preparation method and a use method thereof, wherein the complexes contain copper, silver, gold, cobalt, ruthenium, rhodium, platinum, palladium, nickel, osmium, and/or indium, and methods for making and using same are described herein. In certain embodiments, the metal complexes described herein may be used as precursors to deposit metal or metal-containing films on a substrate through, for example, atomic layer deposition or chemical vapor deposition conditions.

Description

The title complex of volatile metal beta-ketoiminate and metal beta-diimine salt

The cross reference of related application

The application requires the rights and interests of the U.S. Provisional Application No.60/640338 of submission on December 30th, 2004.

Background technology

Semi-conductor industry at electron device such as for example having adopted metallic cross tie part in the prior art microprocessor, such as copper (Cu).Metallic cross tie part can be the lametta that embeds, and forms 3D grid, and millions of the transistors at microprocessor center are by this grid communication and carry out complex calculations.In these and other is used, because copper is excellent electric conductor, so compare such as for example aluminium with other metal, can selects copper or its alloy, thereby obtain having the more high-speed interconnect spare of larger current carrying capacity.

Interconnection vias in the electron device normally prepares by damascene process An, and the photolithography of passing through in dielectric insulator forms on pattern and etched passage and the through hole whereby, is coated with the thin conforma layer that is covered with diffusion barrier material.Diffusion impervious layer usually and metal or copper layer be used for together preventing owing to the interaction of metal or copper layer and unicircuit other parts or the deleterious effect that diffusion causes.Exemplary blocking material includes but not limited to carbide, nitride, carbonitride, silicon carbide, silicon nitride and the carbonitride of silicium of titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, vanadium and/or platinum and these materials and contains the alloy of these materials.In some method, such as when for example cross tie part comprises copper, before filling these features fully with fine copper, can apply thin copper " seed crystal (seed) " or " stopping (strike) " layer at diffusion impervious layer.In other cases, the inculating crystal layer of copper can replace or adds similar cobalt or similar film " glue (g1ue) " layer with similar cobalt or similar film " glue (glue) " layer.Subsequently, can adopt cmp method to remove excessive copper.Because minimal characteristic width to be filled may be less than 0.2 micron, the degree of depth but may be greater than 1 micron, so preferred employing can these features of uniform filling and the sputtering of metals technology that do not stay any hole (hole may cause the finished product that electricity occurs lost efficacy) is come copper seed crystal layer, copper glue-line and/or diffusion impervious layer.

Adopted several different methods to deposit metallic layer such as ionized metal plasma (IMP), physical vapor deposition (PVD), chemical vapour deposition (CVD), ald (ALD), plasma auxiliary chemical vapor deposition (PACVD), plasma modification chemical vapour deposition (PECVD), plating and plated film, such as flash coating, diffusion impervious layer and/or other layer.Wherein, adopting the CVD of one or more Organometallic precursors and ALD method may be the most promising method, because these methods cover for high aspect ratio structures provides the excellent stage, and has good filling through hole characteristic.In typical CVD method, the steam that will contain the volatility Organometallic precursor of required metal is incorporated into matrix surface, at this chemical reaction occurs, and causes the film at this metal of matrix deposition inclusion compound form or pure element form.Because metal is carried with the steam form as volatile precursor usually, so this metal can arrive vertical surface and horizontal surface, obtains equally distributed film.In typical ALD method, volatility Organometallic precursor and reagent gas enter reactor with the ALT pulse form, thereby the certainly limit alternating monolayers of precursors to deposit/reagent on matrix, wherein said individual layer one reacts and forms metallic membrane or metallic film, and this film is reduced into subsequently metal or uses with sedimentation state.For example, if in the ALD method copper Organometallic precursor and suitable oxidant reaction, the Red copper oxide of gained or cupric oxide single or multiple lift can be used for semiconductor application so, perhaps are reduced into the copper metal.

With regard to the copper film, be applicable in the same precursor of CVD and other deposition method some and also can be suitable for and make the ALD precursor.In some applications, following situation may be preferred: precursor has high volatile volatile, the deposition basically be pure (namely, purity about 95% or about 99% or higher) copper film, and/or make the material that may cause polluting enter reaction chamber or the amount that arrives diffusion barrier or other lower surface minimizes.And in these were used, it may be preferred that copper film and diffusion impervious layer have good adhesive property, and delamination and other situation appear in copper film in CMP (Chemical Mechanical Polishing) process because binding property missionary society causes.

For by aforesaid method, especially CVD or ALD method, deposit the low resistance copper film, researched and developed several Organometallic precursors.The copper Organometallic precursor family of two kinds of broad research of often using is Cu (I) and Cu (II) precursor.A kind of Cu (I) precursor commonly used is that general formula is the precursor of " Cu (I) is (W) (hfac) ", wherein " hfac " expression 1,1,1,5,5,5-hexafluoro-2,4-pentanediol salt anionic, (W) expression indifferent equilibrium part is such as for example alkene, alkynes or trialkyl phosphine.Have above-mentioned general formula Cu (I) precursor-individual object lesson is 1,1,1,5,5,5-hexafluoro-2,4-pentanediol copper (I) trimethyl-ethylene base silane (being designated as later on Cu (hfac) (tmvs)) is by Air Products and Chemicals, Inc., Allentown, PA is with trade name CUPRASELECT ^TMSell, described company is the application's assignee.These Cu (I) precursor can pass through the disproportionation deposited film, and wherein two of precursor molecules react at the matrix surface of heating, obtain free ligand (W) and the volatile byproducts Cu of copper metal, two molecules ⁽⁺²⁾(hfac) ₂Reaction formula (1) provides the example of disproportionation reaction:

(1)2Cu ⁽⁺¹⁾(hfac)W→Cu+Cu ⁽⁺²⁾(hfac) ₂+2W

In the CVD deposition, the disproportionation reaction that reaction formula (1) illustrates is carried out at about 200 ℃ usually; But other temperature also can be used, and specifically depends on deposition method.Shown in reaction formula (1), Cu ⁽⁺²⁾(hfac) ₂Consisted of the byproduct of this reaction, may need from reaction chamber, to remove.

Cu (I) precursor of another kind of type is that general formula is the precursor of " (Y) Cu (Z) ".In these concrete Cu (I) precursors, " Y " is organic anion, and " Z " is the indifferent equilibrium part, such as for example trialkyl phosphine.The example of this precursor is CpCuPEt ₃, wherein Cp is cyclopentadienyl, PET ₃It is triethyl phosphine.Under typical CVD condition, two in these precursor molecules can be reacted in wafer surface, whereby two stable trialkyl phosphine Z parts and copper center disassociation, and two (Y) parts are coupled, and copper (I) center is reduced into the copper metal.Whole reaction is shown in reaction formula (2).

(2)2(Y)Cu(Z)→2Cu+(Y-Y)+2(Z)

But in some cases, such chemistry may bring problem, and this is because the trialkyl phosphine ligand that discharges may be polluted reaction chamber and serve as undesirable N-type silicon dopant.

As previously mentioned, to be used for depositing the precursor of copper-containing film be Cu (II) precursor to another kind.Different with Cu (I) precursor, Cu (II) precursor requires to use outside reductive agent, such as for example hydrogen or alcohol, deposits the copper film that is substantially free of impurity.The example of typical case Cu (II) precursor has chemical formula Cu (II) (Y) ₂, wherein (Y) is organic anion.The example of this type precursor includes but not limited to Cu (II) (beta diketone (diketonate)), Cu (II) two (beta-diimines) and Cu (II) two (beta-ketimine) compound.Reaction formula (3) provides wherein hydrogen as the example of the deposition reaction of reductive agent.

(3)Cu(II)(Y) ₂+H ₂→Cu+2YH

Cu (II) precursor is solid normally, and deposited film is temperature required usually above 200 ℃.

Although copper precursors is widely used as cross tie part, other metal or alloy also is used as film in electron device.The example of these metals comprises silver (Ag), gold (Au), cobalt (Co), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), nickel (Ni), osmium (Os), indium (In) and its alloy.

Summary of the invention

Describe below metal complexes with and preparation and the method used, such as for example as the precursor in the deposition method.On the one hand, the invention provides the metal complexes of a kind of formula (I) expression:

Wherein M is the metal that is selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni and Os;

Wherein X is selected from oxygen and NR ⁵

Wherein, R ¹, R ², R ³And R ⁵Each independently is selected from hydrogen atom; Halogen atom; General formula is NO ₂Nitro; General formula is C _nH _2n+1Alkyl, wherein n is the numeral of 1-20; General formula is C _nH _xF _yFluoroalkyl, wherein (x+y) and that equal (2n+1) and, and n is the numeral of 1-20; General formula is (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The aryl that contains 6-12 carbon atom; The aryl that contains the alkyl replacement of 6-12 carbon atom; The aryl that contains the fluoroalkyl replacement of 6-12 carbon atom; The fluoro aryl that contains 6-12 carbon atom; General formula is (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are the numeral of 1-20 independently; General formula is (C _nH _xF _y) O (C _mH _wF _z) fluorine ether, (x+y)=2n wherein, (w+z)=(2m+1), each is the numeral of 1-20 independently for n and m; General formula is (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Each is the aryl that contains the alkyl of 1-20 carbon atom or contain 6-12 carbon atom independently; The alkoxyl group that contains 1-20 carbon atom; With the acid amides that contains 1-20 carbon atom;

R wherein ⁴Being selected from general formula is C _nH _2n+1Alkyl, wherein n is the numeral of 1-20; General formula is C _nH _xF _yFluoroalkyl, wherein (x+y) and that equal (2n+1) and, and n is the numeral of 1-20; General formula is (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The aryl that contains 6-12 carbon atom; The aryl that contains the alkyl replacement of 6-12 carbon atom; The aryl that contains the fluoroalkyl replacement of 6-12 carbon atom; The fluoro aryl that contains 6-12 carbon atom; General formula is (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are the numeral of 1-20 independently; General formula is (C _nH _xF _y) O (C _mH _wF _z) fluorine ether, (x+y)=2n wherein, (w+z)=(2m+1), each is the numeral of 1-20 independently for n and m; General formula is (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Each is the aryl that contains the alkyl of 1-20 carbon atom or contain 6-12 carbon atom independently; The alkoxyl group that contains 1-20 carbon atom; With the acid amides that contains 1-20 carbon atom, and R wherein ⁴Be connected with L by removing hydrogen, atom or group;

Wherein L is selected from following part: the alkyl nitrile that contains 2-20 carbon atom; General formula is (R ⁸) ₃The silyl nitrile of SiCN, wherein R ⁸Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The alkynes that contains 1-20 carbon atom; General formula is (R ⁹) ₃SiCCR ¹⁰Silyl alkynes, R wherein ⁹Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently, R ¹⁰Be hydrogen, contain alkoxyl group, acid amides or the alkyl of 1-20 carbon atom; General formula is (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silyl alkynes, R wherein ¹¹Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently; The alkene, diene or the triolefin that contain 1-20 carbon atom; General formula is (R ¹²) ₃SiCR ¹³C (R ¹³) ₂Silyl alkene, R wherein ¹²Each is alkyl, alkoxyl group, aryl, vinyl or the acid amides that contains 1-20 carbon atom independently, R ¹³Each is hydrogen independently, contains the alkyl of 1-20 carbon atom, perhaps contains the aryl of 6-12 carbon atom; General formula is (R ¹⁴) ₃SiCR ¹³CR ¹³Si (R ¹⁴) ₃Two (silyl) alkene, wherein R ¹⁴Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently, R ¹³Each is hydrogen atom or the alkyl that contains 1-20 carbon atom independently; The propadiene that contains 3-20 carbon atom; General formula is (R ¹⁵) ₂CCC (R ¹⁵) ₂Propadiene, R wherein ¹⁵Each is that hydrogen atom or general formula are (R independently ¹⁶) ₃The alkyl silane of Si, wherein R ¹⁶Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently; General formula is R ¹⁷The alkyl isocyanide of NC, wherein R ¹⁷It is the alkyl that contains 1-20 carbon atom; General formula is (R ¹⁸) ₃The silyl isocyanides of SiNC, wherein R ¹⁸Each is the alkyl that contains 1-20 carbon atom independently, and contains the aryl of 6-12 carbon atom, and wherein L by removing hydrogen, atom or group and R ⁴Link to each other; With

Wherein the organo-metallic key between M and L is selected from two singly-bounds or a singly-bound.

On the other hand, provide a kind of method at the metallic film of matrix deposition, having comprised: make substrate contact have the metal complexes of above-mentioned general formula (I), wherein this contact condition of carrying out is enough to make this title complex reaction and forms film.

On the other hand, provide a kind of electron device that comprises metallic film, wherein said film adopts the metal complexes with above-mentioned general formula (I) to deposit.

Aspect another, a kind of method for preparing the metal complexes with above-mentioned general formula (I) is provided, wherein X is oxygen, comprising: preparation has general formula H ₂NR ⁴The primary amine of L, wherein R ⁴With L as mentioned above; Making general formula is R ¹C (O) CHR ²C (O) R ³Beta-diketon and primary amine polycondensation, form and to have general formula R ¹C (O) CHR ²CNR ⁴LR ³And R ¹, R ², R ³, R ⁴With the aforesaid beta-ketimine intermediate product of L, and make this beta-ketimine intermediate product deprotonation with alkali existing under the condition of source metal, form metal complexes.

On the other hand, provide preparation to have the method for the metal complexes of above-mentioned general formula (I), wherein X is oxygen, comprising: the polycondensation general formula is H ₂NR ⁴Amine and general formula be R ¹C (O) CHR ²C (O) R ³Beta-diketon, the formation general formula is R ¹C (O) CHR ²CN (R ⁴) R ³And R ¹, R ², R ³And R ⁴Beta-ketimine product in the middle of aforesaid first; Make part (L) be attached to this R in beta-ketimine product in the middle of first ⁴, obtaining general formula is R ¹C (O) CHR ²CNR ⁴LR ³Second in the middle of beta-ketimine product, wherein R ¹, R ², R ³, R ⁴With L as mentioned above; Exist under the condition of source metal with making this second beta-ketimine intermediate product deprotonation, the formation metal complexes.

Description of drawings

Fig. 1 provides one of metal complexes described herein or Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me) and example arrangement.

Fig. 2 provides another embodiment or Cu (MeC (O) CHC (NCH of metal complexes described herein ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me) and example arrangement.

Embodiment

The below will describe metal complexes, particularly copper (I) title complex and preparation and application thereof.Metal complexes can come by various deposition methods as for example precursor, comprises CVD or ALD method depositing metallic films or metallic film.

Metal complexes described herein has one or more favourable character owing to having unique structure.Compare with other organometallic metal precursor, metal complexes described herein has relatively high thermostability and relative high chemical reaction ability concurrently, and the combination of these two kinds of character makes it to as CVD and ALD precursor, and especially the ALD precursor is desirable.For the CVD system, ideal situation is that precursor only reacts at the matrix surface of heating, rather than reacts in carrying steam and/or Processing Room.For the ALD system, ideal situation is that metal precursor reacts at specific position, can not be subject to simultaneously the impact of undesirable thermal ageing of occurring in delivery of steam and/or Processing Room.Metal complexes described herein has relatively high thermostability, and this can be transported in CVD or the ALD reactor with stable state steam form.Under this mode of connection, we believe because ligand L is attached directly on ketoimine or the diimide ligand, so being not easy to dissociate from metal center (M), part becomes free molecule, tend to like this in low pressure and the heat condition of the ligand L that usually is enough to dissociate fully under, keep the coordination relation of ligand L and this metal center.The similar title complex that this and L only are bonded to metal center is opposite.In replaceable embodiment, the substituent R that ketoimine or diimide ligand and ligand L are associated ⁴Can carry out the chemical engineering processing, thereby so that under correct processing condition this association can break or dissociate and effectively discharge ligand L.Term used herein " association " refers to connect ketoimine or diimide ligand with ligand L, can include but not limited to that chemical bond (for example, covalent linkage, hydrogen bond etc.), electrostatic attraction, Lewis acid-Lewis base interact, and/or other method.In these embodiments and be enough to discharge under the processing condition of ligand L, can allow for example title complex disproportionation, form metallic membrane or containing metal film.And, R ⁴Precursor can be reduced into small molecular weight unit, easier desorption in the process that this unit is processed with the disassociation of ligand L in for example CVD or ALD reactor.For example, if precursor and water fully react, the result of disassociation will be the growth of copper oxide and the small molecular weight volatility part fragment that discharges hydrolysis so.For example, metal complexes Cu (Me (C (O) CHC (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me) (the C in the title complex wherein ₂H ₃Group represents vinyl) and water reaction to generate solid oxidation cuprous, MeC (O) CH ₂C (NCH ₂CH ₂NMeH) Me, and C ₂H ₃Me ₂SiOH, the latter generation tetramethyl divinyl disiloxane that is coupled.

Another specific characteristic of these title complexs is that they can be provided at that the space exposes more metal center on face of precursor.Typical beta-ketimine or beta-diketon olefin(e) compound are flat molecules, and wherein coordination diketone (diketomate) or ketoiminate (ketoiminate) negatively charged ion, metal center and alkene all are positioned at same plane.Different therewith, title complex described herein can allow the coordination plane of title complex to become the arc of protrusion, metal center is pushed to all the more below the title complex, thereby made it expose manyly, easier arrival surface and reagent molecule.For example, at illustrative metal title complex Cu (Me (C (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me) in, the beta-ketoiminate chelate ring tilts to depart from about 7 degree of copper alkene coordination trilateral, thus it is more that copper is exposed below molecule.For the method for some ALD and CVD type, this exposure and consequent space access (access) may be important, because the copper atom that helps so wherein to comprise is adsorbed onto on the matrix surface.And, by control R ⁴The essence of association ligand L and length can be developed the relatively metal precursor of tension of conformation, thereby the metal center of exposure is provided.By chemistry fracture or disassociation R ⁴With ligand L be connected to discharge strain, obtained relatively high reactivity.In other words, by adjusting the structure of these precursors, should make up this title complex, its internal strain can be by fracture R ⁴Connect and discharge, drive molecular breakdown and become the little organic unit of volatility, thereby the metal center that provides simultaneously the space to expose obtains high surface reaction and metal deposition.

Metal complexes described herein has following general formula (I):

In general formula (I), M is the metal that is selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni and Os.In certain embodiments, atoms metal M is copper.In general formula (I), X can be oxygen, thereby forms ketoiminate complexes, and perhaps replacedly X can be NR ⁵Thereby, form the diimmonium salt title complex.In general formula (I), substituent R ¹, R ², R ³And R ⁵Each independently is selected from hydrogen atom; Halogen atom; General formula NO ₂Nitro; General formula C _nH _2n+1Alkyl, wherein n is the numeral between the 1-20; General formula C _nH _xF _yFluoroalkyl, wherein (x+y) and that equal (2n+1) and, and n is the numeral between the 1-20; General formula is (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The aryl that contains 6-12 carbon atom; The aryl that contains the alkyl replacement of 6-12 carbon atom; The aryl that contains the fluoroalkyl replacement of 6-12 carbon atom; The fluoro aryl that contains 6-12 carbon atom; General formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are the numeral of 1-20 independently; General formula is (C _nH _xF _y) O (C _mH _wF _z) fluorine ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m each be the numeral of 1-20 independently; General formula is (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Each is the aryl that contains the alkyl of 1-20 carbon atom or contain the 6-12 carbon atom independently; The alkoxyl group that contains 1-20 carbon atom; With the acid amides that contains the 1-20 carbon atom.In general formula (I), substituent R ⁴Being selected from general formula is C _nH _2n+1Alkyl, wherein n is the numeral of 1-20; General formula C _nH _xF _yFluoroalkyl, wherein (x+y) and that equal (2n+1) and, and n is the numeral of 1-20; General formula is (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The aryl that contains 6-12 carbon atom; The aryl that contains the alkyl replacement of 6-12 carbon atom; The aryl that contains the fluoroalkyl replacement of 6-12 carbon atom; The fluoro aryl that contains the 6-12 carbon atom; General formula is (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are the numeral of 1-20 independently; General formula is (C _nH _xF _y) O (C _mH _wF _z) fluorine ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m each be the numeral of 1-20 independently; General formula is (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Each is the aryl that contains the alkyl of 1-20 carbon atom or contain 6-12 carbon atom independently; The alkoxyl group that contains 1-20 carbon atom; With the acid amides that contains 1-20 carbon atom, and R wherein ⁴In removed behind hydrogen, atom or the group and L associates.And in formula (I), L is selected from following part: the alkyl nitrile that contains 2-20 carbon atom; General formula is (R ⁸) ₃The silyl nitrile of SiCN, wherein R ⁸Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently; The alkynes that contains 1-20 carbon atom; General formula is (R ⁹) ₃SiCCR ¹⁰Silyl alkynes, R wherein ⁹Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently, and R ¹⁰Be hydrogen, contain alkoxyl group, acid amides or the alkyl of 1-20 carbon atom; General formula is (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silyl alkynes, R wherein ¹¹Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently; The alkene, diene or the triolefin that contain 1-20 carbon atom; General formula is (R ¹²) ₃SiCR ¹³C (R ¹³) ₂Silyl alkene, R wherein ¹²Each is alkyl, alkoxyl group, vinyl, aryl or the acid amides that contains 1-20 carbon atom independently, and R ¹³Each is hydrogen or the alkyl that contains 1-20 carbon atom independently; General formula is (R ¹⁴) ₃SiCR ¹³CR ¹³Si (R ¹⁴) ₃Two (silyl) alkene, wherein R ¹⁴Each is alkyl, alkoxyl group or the acid amides that contains 1-20 carbon atom independently, and R ¹³Each is hydrogen atom or the alkyl that contains 1-20 carbon atom independently; The propadiene that contains 3-20 carbon atom; General formula is (R ¹⁵) ₂CCC (R ¹⁵) 2 propadiene, wherein R ¹⁵Each is that hydrogen atom, general formula are (R independently ¹⁶) ₃The alkyl silane of Si, wherein R ¹⁶Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently; General formula is R ¹⁷The alkyl isocyanide of NC, wherein R ¹⁷It is the alkyl that contains 1-20 carbon atom; General formula is (R ¹⁸) ₃The silyl isocyanides of SiNC, wherein R ¹⁸Each is alkyl, acid amides or the alkoxyl group that contains 1-20 carbon atom independently; With the aryl that contains 6-12 carbon atom, and wherein L has removed behind hydrogen, atom or the group and R ⁴Associate.

Term used herein " alkyl " comprises straight chain, side chain or cycloalkyl, contains 1-20 carbon atom or 1-10 carbon atom.Exemplary alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-pentyl, n-hexyl, cyclopentyl and cyclohexyl.Term " alkyl " also is applied to the moieties that is contained in other group, such as fluoroalkyl, alkylhalide group, alkylaryl or arylalkyl.Term used herein " aryl " comprises the 6-12 unit carbocyclic ring with aromatic character.Exemplary aryl comprises phenyl and naphthyl.Term " aryl that alkyl replaces " refers to the aryl moiety with the alkyl replacement.The aryl that the alkyl of exemplary type replaces comprises tolyl and xylyl.Term " halogen " and " halogen " comprise fluorine, chlorine, bromine or iodine.Term " fluoroalkyl " refers to the moieties that wherein one or more hydrogen atoms are replaced by the fluorine halogen atom, can partly or entirely fluoridize, and comprises the straight chain, side chain or the ring fluorinated alkyl that contain 1-20 carbon atom or 1-10 carbon atom.Exemplary fluoroalkyl comprises-CF ₃,-CF ₂CF ₃,-CH ₂CF ₃,-CF ₂CFH ₂Perhaps-CH ₂CF ₂CF ₃In certain embodiments, some group discussed herein can be replaced such as O, N, Si or S such as for example halogen atom or other heteroatoms by one or more other elements.

In general formula (I), select substituent R ⁴Can associate with ligand L.In addition, select ligand L can and R ⁴Associate.Believe ligand L and substituent R ⁴There are hydrogen, atom or group to be removed so that R ⁴Can associate with L, thereby make ligand L connect copper imines or the diimide ligand of title complex.In this connection, when L is silyl alkene, its key can with R ⁴Associate.Exemplary such as Fig. 1 or Cu (Me (C (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me).In this embodiment, X is oxygen, and the general formula of L is H ₂C=CHSiMe ₂, R ⁴OCH ₂CH ₂, R ³Hydrogen, R ¹And R ²It all is methyl.NR at another X ⁵Embodiment in, R ⁵Can associate with L.In this embodiment, ligand L and substituent R ⁵All have hydrogen, atom or group and be removed, so that R ⁵With L can be with R ⁴The association mode identical with L associated.

In certain embodiments, substituent R ⁴Also can be connected to substituent R ¹, R ²And/or R ³On.In these embodiments, work as R ¹, R ²And/or R ³Neither hydrogen atom, halogen atom are not again nitro NO ₂The time, substituent R ⁴Can be only and substituent R ¹, R ²And/or R ³Connect.

In some title complex embodiment as herein described, X is NR ⁵And R ⁵Can be R ¹, R ²Or R ³Above-mentioned any group or the atom of expression.In these embodiments, part (L) perhaps can be the other part (L) of any above-mentioned group or atom, also can be attached to substituent R ⁵And substituent R ⁴On.In these embodiments, believing that at least one ligand L has for example can be used to and R ⁵The valency that associates, thus make ligand L connect the diimide ligand of title complex.In this or other embodiment, substituent R ⁵Also can be connected to R ¹, R ², R ³And/or R ⁴One of any or all, form ring structure.In a rear embodiment, only work as R ¹, R ²And/or R ³Neither hydrogen atom, halogen atom are not again nitro NO ₂The time, perhaps replacedly work as R ⁵When being hydrogen atom, substituent R ⁵And R ¹, R ²And/or R ³Connect.

In certain embodiments, substituent R ⁴And/or optional substituent R ⁵If (X is NR ⁵) can adjust, so that the metal center coordination of the metal center of ligand L and adjacent part rather than its oneself.In these embodiments, can form other title complex such as but not limited to dipolymer, trimer and tetramer title complex.

In certain embodiments, substituent R ¹, R ²And R ³In any one or all can separate connection form ring structure.In certain embodiments, R ¹And R ²And/or R ²And R ³Can separate connection form ring structure.

In certain embodiments, metal complexes described herein can comprise fluorine.In these embodiments, substituent R ¹, R ², R ³, R ⁴And R ⁵One of any or all can comprise fluorine, the fluoro aryl that the fluoroalkyl that aryl, fluoro aryl, the alkyl that replaces such as for example fluoroalkyl, fluoroalkyl replaces or fluoroalkyl replace.In interchangeable embodiment, metal complexes described herein does not comprise fluorine.

In one embodiment, the ligand L in the general formula (I) can be alkyl nitrile, such as but not limited to CH ₂CN or Me ₂CH ₂CCN.In the present embodiment and previous embodiments about L, the definition ligand L group removed hydrogen so that its can and R ⁴Associate.In replaceable embodiment, the ligand L of general formula (I) can be the silyl nitrile, is such as but not limited to Me ₂CH ₂SiCN.In yet another embodiment, the ligand L in the general formula (I) can be alkynes, is such as but not limited to CH ₂CCMe or CH ₂CCH.In another embodiment, the ligand L in the general formula (I) can be alkene, is such as but not limited to Me ₃CCHCH ₂Or Me (CH ₂) ₂CHCH ₂In another embodiment, the ligand L in the general formula (I) can be that general formula is (R ⁹) ₃SiCCR ¹⁰Or (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silyl alkynes, be such as but not limited to Me ₃SiCHCH, Me ₂CH ₂SiCHCHSiMe ₃, (MeO) ₂CH ₂SiCHCH ₂Perhaps (EtO) ₂CH ₂SiCHCH ₂In yet another embodiment, the ligand L of general formula (I) can be propadiene, is such as but not limited to CHCCCH ₂Or MeCCCMe ₂In another embodiment, the ligand L in the general formula (I) can be alkyl isocyanide, is such as but not limited to Me ₂CH ₂CNC.In aforementioned formula and specification sheets full text, term " Me " expression methyl, " Et " represents ethyl, " i-Pr " represents sec.-propyl.

In above-mentioned general formula (I), the organo-metallic key between metal center and the part (L) or 2 singly-bounds, or 1 singly-bound.

In one embodiment, the synthesis mode of the wherein X as herein described metal ketoiminate complexes that is oxygen can be to form the beta-ketimine intermediate product with group L functionalized amine and beta-diketone compound reaction.Described amine can be that for example general formula is H ₂NR ⁴The primary amine of L, wherein R ⁴With L can be above-mentioned arbitrary group or atom.Unrestricted type example with primary amine of above-mentioned general formula comprises H ₂NCH ₂CH ₂OSiMe ₂(C ₂H ₃).Beta-diketon can be that general formula is R ¹C (O) CHR ²C (O) R ³Compound, R wherein ¹, R ²And R ³Each can be above-mentioned arbitrary group or atom independently.Non-limitative example with beta-diketone compound of above-mentioned general formula is 2,4-diacetylmethane, 1,1,1-three fluoro-2,4-diacetylmethane, 2,4-hexanedione and 3,5-heptadione.An example can be with amine H ₂NCH ₂CH ₂OSiMe ₂(C ₂H ₃) and 2,4-diacetylmethane reaction formation beta-ketimine intermediate product MeC (O) CH ₂C (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me.In case prepared the beta-ketimine intermediate product, deprotonation (that is, removing acid proton) occurs in it, then exists under the condition of alkali and the source metal complexing, obtains having the title complex of above-mentioned general formula (I).

In another embodiment, wherein X is NR as mentioned above ⁵Metal diimmonium salt Complex synthesis mode described herein can be to prepare at first as mentioned above the beta-ketimine intermediate product, then use alkylating agent such as triethyl oxygen It processes a tetrafluoro borate or dimethyl sulfate salt pair, then with gained compound and R wherein ⁵Aforesaid R ⁵NH ₂Reaction obtains beta-diimine salt [R ¹C (R ⁵NH) CHR ²C (NR ⁴L) R ³] ⁺[V] ^-As the second intermediate product, wherein V is that the conjugate base of alkylating agent is (for example, when adopting triethyl oxygen

During a tetrafluoro borate, V is the Tetrafluoroboric acid salt anionic).Radicals R ⁵Can maybe cannot be connected with group L.Gained beta-diimine salt part secondary deprotonation then with the source metal complexing, obtains having the title complex of above-mentioned general formula (I).

The reaction of amine and beta-diketone compound can be carried out existing under the condition of solvent.Suitable solvent includes but not limited to independent ether (for example, Anaesthetie Ether (Et ₂O), tetrahydrofuran (THF) (" THE "), di-n-butyl ether, Isosorbide-5-Nitrae-two Alkane or ethylene glycol dimethyl ether); Nitrile (CH for example ₃CN); Perhaps aromatic substance (for example, toluene) or its mixture.In certain embodiments, solvent is THF.Temperature of reaction can be from-78 ℃ to solvent boiling point.Reaction times can or namely be carved into about 48 hours from about 0 hour, perhaps from about 4 hours to about 12 hours.In certain embodiments, intermediate product can carry out purifying such as distillation, distillation chromatography, recrystallization and/or grinding by standard step.But in some embodiment, the reaction of amine and beta-diketone compound can be carried out under the condition of solvent not having, if especially gained beta-ketimine intermediate product is in the situation of liquid.

In certain embodiments, beta-ketimine or beta-diimine intermediate product are until final metal complexes can be to have one or more in following general formula (II), (III) or following three tautomers (IV):

In above-mentioned general formula, variable R ¹, R ², R ³, R ⁴, X and part (L) can each be any atom as herein described or group independently.

Middle beta-ketimine product may need activation before obtaining beta-diimine with amine or ammonia react.For example, middle beta-ketimine product may at first need to be by triethyl oxygen A tetrafluoro borate or Dimethylsulfate alkylation.

Reaction formula (IV) has provided the example of an embodiment of preparation metal as herein described or Cu (I) ketoiminate complexes.In this embodiment, Cu (I) title complex is by adopting one or more alkali to make the beta-ketimine intermediate product deprotonation that is reacted gained by amine and beta-diketone compound, perhaps make the beta-diimine intermediate product deprotonation by beta-ketimine intermediate product and amine or ammonia react gained, then and Cu (I) chelating, obtain respectively beta-ketimine or beta-diimine title complex.The non-limitative example of this reaction is shown in the following reaction formula (4), and this reaction formula has provided the preparation process of beta-ketimine Cu (I) title complex:

Reaction formula (4)

In reaction formula (4), the beta-ketimine intermediate product is the compound of general formula (VI), and itself and alkali are that sodium hydride and copper (I) source are the cupric chloride reaction, make Cu (I) title complex and the sodium-chlor of general formula (I).Other alkali that can be used for above-mentioned reaction includes but not limited to lithium hydride, n-Butyl Lithium, potassium hydride KH, two (trimethyl silyl acid amides) sodium, LDA and potassium tert.-butoxide etc.Other copper (I) source that can be used for above-mentioned reaction includes but not limited to cupric bromide (I), cupric iodide (I), trifluoroacetic acid copper (I), copper triflate (I) benzene (benxene) adducts, pure copper (I), amination copper (I), venus crystals (I), phenol copper (I), copper (I) ethanamide and-oxyl copper (I).Prepare therein in the embodiment of other metal or hybrid metal title complex, source metal is one or more metal-salts that contain required metal M.The expectation productive rate of metal or Cu (I) title complex can be about 5%-about 95% of theoretical yield.In certain embodiments, final product or metal complexes such as Cu (I) title complex, can carry out purifying such as distillation, distillation, chromatography, recrystallization and/or grinding by standard step.

Replacedly, the preparation of metal complexes of the present invention can be at first to synthesize other similar metal two (ketoimine) and two (diimine) compounds of metal, then with the source metal reaction or with source metal it is reduced.Other replaceable approach of synthetic these precursors also is feasible, shown in the non-limiting case that provides among the embodiment below.

In interchangeable embodiment, the beta-ketimine intermediate product can be directly and source metal, such as aryl copper (I) (for example

Copper) or pure copper (for example [CuOt-Bu] ₄) react, form metal or Cu (I) title complex.In yet another embodiment, metal complexes can be consisting of part in suitable electrochemical method, i.e. beta-ketimine intermediate product and atoms metal preparation.These identical route of synthesis can be used for synthesizing metal diimmonium salt title complex.

The another example of present method is thanomin (H ₂NCH ₂CH ₂OH) and 2,4-diacetylmethane reaction, obtain first in the middle of beta-ketimine product MeC (O) CH ₂C (NCH ₂CH ₂OH) Me.This first middle beta-ketimine product MeC (O) CH ₂C (NCH ₂CH ₂OH) Me and Chlorodimethyl vinyl silanes reaction obtains the second middle beta-ketimine product MeC (O) CH ₂C (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me.This in the middle of second beta-ketimine product deprotonation and with the copper complexing, obtain title complex Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃) Me).

As previously mentioned, metal complexes described herein can be used as the film that precursor is used for depositing at matrix cupric.The example of suitable matrix includes but not limited to semiconductor material such as gallium arsenide (" GaAs "), boron nitrogenize (BN) silicon and contains the composition of silicon, such as silicon metal, polysilicon, amorphous silicon, epitaxially grown silicon, silicon-dioxide (" SiO ₂"), silicon carbide (" SiC "), siloxicon (" SiOC "), silicon nitride (" SiN "), carbonitride of silicium (" SiCN "), silicone glass (" OSG "), organic fluorinated silicone silicate glass (" OFSG "), fluorosilicate glass (" FSG "), and other suitable matrix or its mixture.Matrix can also comprise multiple layer, on these layers, can apply film such as for example antireflection coatings, photoresist material, organic polymer, porous organic material and inorganic materials, metal such as copper and aluminium, perhaps diffusion impervious layer.Metal complexes can adopt arbitrary deposition techniques described herein or known in the art.The exemplary deposition technology includes but not limited to chemical vapour deposition (CVD), ald (ALD), plasma auxiliary chemical vapor deposition (PACVD) and plasma modification chemical vapour deposition (PECVD).

In certain embodiments, these title complexs can be used to the film by CVD or ALD and suitable agent reaction generation metal or its alloy.In interchangeable embodiment, metal complexes can react by disproportionation reaction, and metallic membrane or metallic film are provided.In another embodiment, metal complexes can exist under the condition of reductive agent reaction to obtain metallic membrane or metallic film.For example, in one embodiment, and the reaction of halogen source reagent can form the film of metal halide, yet in another embodiment, and suitable oxidizers can provide metal oxide film such as the reaction of water vapour.In another embodiment, and oxidant reaction subsequently again with reductive agent such as H-H reaction, can form metallic membrane or metal/metal oxide hybrid films.Replacedly, copper precursors can with by directly from or be positioned at the plasma-activated reagent gas reaction in remote plasma source downstream.Metal complexes disclosed herein also can be used for mixing with certain combination and other metal precursor, forms metallic film, metallic film and/or metal alloy film.These films can use with sedimentation state, perhaps replacedly can be reduced into suitable reductive agent required metal.

In certain embodiments, metal complexes adopts CVD or ALD deposition techniques on matrix.The deposition of Cu (I) title complex can be 400 ℃ or following temperature, and perhaps 200 ℃ or following, perhaps 100 ℃ or following carrying out.In typical CVD deposition method, the metal complexes that will have general formula (I) is introduced reaction chamber such as in the vacuum chamber.In some embodiment, can be before introducing metal complexes, among and/or afterwards, introduce other chemical reagent except this metal complexes.The energy for metal complexes and optional chemical reagent provide energy, thereby forms film at least part of matrix such as for example heat energy, plasma energy or other energy.

As previously mentioned, in certain embodiments, before metal complexes is introduced reaction chamber, among and/or afterwards, can introduce chemical reagent.The selection of chemical reagent can depend on the composition of required telolemma.For example, in one embodiment, and the reaction of halogen-containing chemical reagent can form the film of metal halide, but in another embodiment, and the reaction of oxygenant chemical reagent can form metal oxide film.Exemplary chemical reagent includes but not limited to that oxygenant (is O ₂, NO, NO ₂, O ₃, CO, CO ₂Deng); Water; Halogenide; Halogen-containing silane; Alkyl chlorosilane, alkyl bromide silane or alkyl iodide silane; Halogenated silicon compound is such as silicon tetrachloride, Silicon bromide or silicon tetraiodide; The tin compound of halogenation is such as alkyl chloride stannane, alkyl bromide stannane or alkyl iodide stannane; The germane compound is such as alkyl chloride germane, alkyl bromide germane or alkyl iodide germane; The boron trihalides compound is such as boron trichloride, boron tribromide or triiodide boron; Aluminum halide compounds is such as aluminum chloride, aluminum bromide or aluminum iodide; Aluminum alkyl halide; Gallium halide is such as gallium trichloride, tribromide gallium or triiodide gallium; Or its combination.It is also contemplated that the derivative that also can use above-claimed cpd.These chemical reagent can directly be transported to reaction chamber with gas form, are transported in the reaction chamber with the solid form of volatile liquid form, distillation and/or by inert carrier gas.The example of inert carrier gas comprises nitrogen, hydrogen, argon gas and xenon etc.

In certain embodiments, metallic membrane can be formed on the matrix surface by disproportionation reaction, such as Cu (I) title complex shown in the following reaction formula (5).

Reaction formula 5

In another embodiment, metallic membrane can be deposited on the matrix surface under the condition of reductive agent existing, and wherein reductive agent is used for for example film being reduced into metal.Metal complexes with general formula (I) can be introduced in CVD or the ALD reactor together with reductive agent.Reductive agent is introduced with gas form usually.The example of suitable reductive agent includes but not limited to hydrogen, alcohol, hydrogen plasma, long-range hydrogen plasma, silicane (that is, diethylsilane, ethylsilane, dimethylsilane, phenyl silane, silane, disilane, aminosilane), boranes (being borine, diboron hexahydride), aluminium alkanes, germane class, hydrazine class, ammonia or its mixture.

In certain embodiments, by Cu (I) the title complex depositing metallic films of ALD deposition method by general formula (I).In typical ALD method, one or more gaseous states or steam attitude precursor are introduced in the Processing Room in the ALT pulse mode in fabrication cycles, in this Processing Room matrix are housed.Preferred each fabrication cycles is by absorption and preferably form the material that is no more than an about individual layer by chemisorption.The number of fabrication cycles of this layer of being used for growing depends on required thickness, but usually can the circulation above 1000.For semiconducter device, repeat fabrication cycles until in the double-metal inlaid structure thickness of blocking layer or inculating crystal layer be enough to carry out its required function.

In the ALD method, the temperature of matrix is arranged on the scope of being convenient to chemisorption, namely lowly highly is enough to avoid the precursor polycondensation and provides enough activation energy for the required surface reaction of each fabrication cycles to enough keeping the material that adsorbs and unaffected while of the bonding between the lower substrate.The Processing Room temperature can be 0 ℃-400 ℃, perhaps 0 ℃-300 ℃, and perhaps 0 ℃-275 ℃.Pressure in the ALD method in the Processing Room can be the 0.1-1000 holder, perhaps 0.1-15 holder, perhaps 0.1-10 holder.But, should be appreciated that can change any concrete ALD technique temperature and pressure, specifically depend on one or more related precursors.

Can be used singly or in combination any one in aforementioned film as herein described and other film known in the art.For example, in one embodiment, then this multilayer is reduced by sequential aggradation oxidation copper film and copper metallic membrane and to obtain the fine copper film, can form and mix the copper-containing film that forms.

In certain embodiments, metal complexes described herein can be dissolved in and form solution in the suitable solvent, described solvent ratio such as amine (for example, triethylamine), ether (for example THF), aromatics (for example toluene) or any other solvent disclosed herein.Gained solution can directly be transported to ALD or CVD reaction chamber with the steam form after the flash distillation of liquid injection (DLI) system.In other embodiments, title complex described herein can before introducing the DLI system, be dissolved in stabilising liq such as alkene or alkynes in.

Embodiment

In the following example, employing is furnished with the 5890 serial 11G.C of Hewlett-Packard of HP-5MS and the G.C.M.S collection of illustrative plates that 5972 series mass are selected the detector measurement sample.The NMR that carries out sample with Bruker AMX500 spectrometer when the 500MHz analyzes.By C ₆D ₆Chemical shift is set, and that 1H is 7.16ppm, ¹³That C is 128.39/1000000ths (ppm).The Bruker D8 platform diffractometer that employing has been equipped with APEX ccd detector and Kryoflex cryostat carries out X-ray analysis.

Embodiment 1: synthetic H ₂NCH ₂CH ₂OSiMe ₂(C ₂H ₃)

80.0ml (0.57mol) Chlorodimethyl vinyl silanes and 79.0ml (0.57mol) triethylamine and 2.0 liters of Ganji's alkane mix, under nitrogen atmosphere in the room temperature strong stirring.In 1 hour time, slowly add 35.0ml thanomin (0.57mol), obtain white viscous paste.Under nitrogen atmosphere, filter out solid triethylamine hydrochloride, clean with other 1.0 liters of Ganji's alkane.Then under atmospheric pressure from product, distill out hexane, obtain 58.0g (70%) product.The NMR result of product is as follows:

¹H?NMR：(5O0MHz，C ₆D ₆)：δ＝0.15(d，6H)，δ＝2.8(q，2H)，δ＝3.5(t，2H)，δ＝5.75(dd，1H)，δ＝5.94(dq，1H)，δ＝6.17(dq，1H).

Embodiment 2: synthetic MeC (O) CH ₂C (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me

With 58.3g (0.40mol) H ₂NCH ₂CH ₂OSiMe ₂(C ₂H ₃) slowly dropwise join and be in room temperature and have excess sulfuric acid sodium and be among the 250ml THF under the whipped state, wherein contain 2 of 40g (0.40mol), 4-diacetylmethane among this THF.Stirred the mixture 4 hours, then stripping is removed THF under vacuum.Then under 120 ℃/20mTorr, distill Residual oil, obtain 35g final product (43% productive rate).The NMR result of product is as follows:

¹H?NMR：(500MHz，C ₆D ₆)：δ＝0.15(s，6H)，δ＝1.40(s，3H)，δ＝2.0(s，3H)，δ＝2.8(q，2H)，δ＝3.27(q，2H)，δ＝4.9(s，1H)，δ＝5.75(m，1H)，δ＝5.95(m，1H)，δ＝6.1(m，1H).

Embodiment 3: synthetic Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me)

With 17.0g (0.075mol) MeC (O) CH ₂C (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me is dissolved in 10.0ml dry tetrahydrofuran (THF) solvent, joining the 100ml that is in whipped state under nitrogen atmosphere in 1 hour time does among the THF, (40% is excessive, and then 1.04mol) sodium hydride at room temperature stirs and spend the night wherein to contain 2.5g among this THF.Under nitrogen atmosphere, filter this mixture, then do in 7.5g (0.075mol) copper (I) muriate that stirs among the THF at 10ml slowly joining in 1 hour time under the nitrogen atmosphere in 0 ℃, this mixture heating up is spent the night to room temperature and stirring.Then stripping is removed THF under vacuum, adds in Ganji's alkane of 500ml deoxidation before filtration, stirs 10 minutes.After stripping is removed hexane under vacuum, obtained the crude product of light blue lenticular, productive rate 15.8g (73%).After the lower distillation of 20mTorr and 70 ℃, obtain being close to colourless, fusing point and be 72.5 ℃ crystal sublimate.The crystal of distillation has carried out X-ray analysis, and final structure as shown in Figure 1.The NMR result of product is as follows:

¹H?NMR：(500MHz，C ₆D ₆)：δ＝0.10(d，6H)，δ＝1.53(s，3H)，δ＝2.14(s，3H)，δ＝3.1(bs，1H)，δ＝3.35(bs，1H)，δ＝3.55(bs，1H)，δ＝3.65(dd，1H)，δ＝3.72(bs，1H)，δ＝3.83(dd，1H)，δ＝4.1(dd，1H)，δ＝4.96(s，1H)； ¹³CNMR：(500?MHz，C ₆D ₆)：δ＝-2.8(s，1C)，δ＝0.3(s，1C)，δ＝22.5(s，1C)，δ＝27.9(s，1C)，δ＝57.1(s，1C)，δ＝65.3(s，1C)，δ＝79.8(s，1C)，δ＝83.2(s，1C)，δ＝98.3(s，1C)，δ＝169.2(s，1C)，δ＝181.4(s，1C).

Embodiment 4:Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me) and replaceable synthesis mode

This synthetic minute two portions carry out:

Partly (a): synthetic MeC (O) CH ₂C (NCH ₂CH ₂OH) Me

With 100.0g (1.0mol) 2, the 4-pentanediol slowly joins in the hexane of 600ml strong stirring, wherein contains 61.0g (1mol) thanomin and the agent of 100g dried over sodium sulfate in this hexane.Mixture finally becomes solid matter, outwells hexane layer.Then the THF that adds 600ml stirs lower slowly this mixture of heating until all solids dissolving except sodium sulfate.Then outwell the THF layer, Slow cooling spends the night with crystallization.Then outwell liquid level, blot solid.Productive rate is 87g or 61%.NMR result shows it is intermediate product:

¹H?NMR(500MHz，C ₆D ₆)：δ＝1.41(s，3H)，δ＝2.0(s，3H)，δ＝2.76(q，2H)，δ＝3.33(t，2H)，δ＝4.83(s，1H)，δ＝11.15(bs，1H).

Partly (b): synthetic Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me)

MeC (O) CH with 40g (0.28mol) ₂C (NCH ₂CH ₂OH) Me is dissolved under nitrogen atmosphere among the dried THF of 500ml, in 6.7g (0.28mol) sodium hydride that is stirring in the THF that slowly is added in 1 hour time at 250ml.Discovery has formed hydrogen, and mixture becomes white viscous paste.The 2.5M n-Butyl Lithium (0.28mol) that adds 112ml in 1 hour time adds the extra THF of 250ml this moment, better mixes.Stirred the faint yellow suspension of gained more than two hour, and in 30 minutes time, added subsequently 33.6g (0.28mol) Chlorodimethyl vinyl silanes, continued to stir the mixture 2 hours.Then under nitrogen atmosphere this thickness suspension is dropwise joined the 50ml that is in whipped state in 1 hour time and do among the THF, described THF is 0 ℃ and contains 29g (0.28mol) copper (I) muriate.Then heated mixt arrives room temperature, and stirs and spend the night.Then stripping is removed THF under vacuum, adds 500ml Ganji alkane under nitrogen atmosphere, stirs the mixture 10 minutes, then filters out hexane from solid.The hexane that adds other 500ml in solid is heated to 45 ℃ and stirred 45 minutes, then filter and and the hexane that extracts for the first time combine.Stripping is removed hexane under vacuum, obtains the light blue coarse crystal product of 52.0g, and percentage yield is 64%.Then sublimation purification crude product under 70 ℃ and 20mTorr.

Embodiment 5: synthetic MeC (O) CH ₂C (NCH ₂CH ₂NMeH) Me

With 20.0g (0.2mol) 2, the 4-pentanediol dropwise joins among the 200ml THF that is in whipped state in 30 minutes time, wherein contains 14.8g (0.2mol) N-methyl ethylene diamine and the agent of 36g dried over sodium sulfate among this THF.The mixture yellowing at room temperature stirred 2 days.Then outwell the THF layer, preserve at the 2A of drying molecular sieve and spend the night, then stripping is removed THF under vacuum, obtains golden brown oil.Productive rate is 25.5g or 82%.The NMR result of product is:

¹H?NMR(500MHz，C ₆D ₆)：δ＝1.45(s，3H)，δ＝2.03(s，3H)，δ＝2.05(s，3H)，δ＝2.25(t，2H)，δ＝2.74(q，2H)，δ＝4.88(s，1H)，δ＝11.1(bs，1H).

Embodiment 6: synthetic MeC (O) CH ₂C (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me

MeC (O) CH with 51.0g (0.327mol) ₂C (NCH ₂CH ₂NMeH) Me joins to be among the 1 liter of dried THF that stirs under the nitrogen atmosphere in 1 hour time and obtains creamy thickness suspension, wherein contains the potassium hydride KH of 13.1g (0.327mol) among this THF.In 30 minutes time, to the Chlorodimethyl vinyl silanes that wherein adds 45ml (0.327mol), then continued to stir the mixture 2 hours.Then stripping is removed THF under vacuum, adds 1 liter of Ganji's alkane, stirs 10 minutes.Then filter this suspension, clean this solid 3 times with the other hexane of 50ml.All hexane cleaning materials are combined, and then stripping obtains the golden brown oil of 62.3g or 80% productive rate, and then vacuum distilling should oil under 120 ℃ and 20mTorr.The NMR result of product is:

¹H?NMR(500MHz，C ₆D ₆)：δ＝0.18(s，6H)，δ＝1.44(s，3H)，δ＝2.04(s，3H)，δ＝2.24(s，3H)，δ＝2.57(t，2H)，δ＝2.71(q，2H)，δ＝4.9(s，1H)，δ＝5.7(dd，1H)，δ＝5.94(dd，1H)，δ＝6.2(dd，1H)，δ＝11.1(bs，1H).

Embodiment 7: synthetic Cu (MeC (O) CHC (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me)

MeC (O) CH with 6.1g (0.025mol) ₂C (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me joining under nitrogen atmosphere among the dried THF of the 175ml that is in whipped state in 30 minutes time, and stirred 2 hours, contain 1.02g (0.025mol) potassium hydride KH among the wherein said THF.Then filter this slightly slightly turbid solution and dropwise join the 10ml that is under the nitrogen atmosphere and constantly stirs in 3 hours time and do among the THF, described THF is in 0 ℃ and contain in copper (I) muriate of 2.5g (0.025mol).Then heated mixt is to ambient temperature overnight.Then then this THF of stripping under vacuum adds Ganji's alkane of 200ml under nitrogen atmosphere, mixture stirs and then filtered in 5 minutes.Stripping obtains the shallow aquamarine crystal of 6.3g crude product after removing hexane, perhaps 83% productive rate, then sublimation purification under 75 ℃ and 20mTorr.The product fusing point is 86 ℃.Crystal after the distillation has carried out X-ray analysis, and the result as shown in Figure 2.The NMR result of product is as follows:

1H NMR:(500MHz, C ₆D ₆): δ=0.05 (bs, 6H), δ=1.65 (s, 3H), δ=2.16 (s, 3H), δ=2.27 (s, 3H), δ=2.47 (bs, 1H), δ=2.76 (bs, 1H), δ=3.11 (bs, 1H), δ=3.21 (bs, 1H), δ=3.78 (dd, 1H), δ=4.0 (dd, 1H), δ=4.21 (dd, 1H), δ=5.01 (s, 1H); With ¹³CNMR:(500 MHz, C ₆D ₆): δ=-0.05 (bs, 1C), δ=-2.5 (bs, 1C), δ=23.4 (s, 1C), δ=27.9 (s, 1C), δ=34.9 (s, 1C), δ=51.6 (s, 1C), δ=53.0 (s, 1C), δ=81.2 (s, 1C), δ=84.1 (s, 1C), δ=170.1 (s, 1C), δ=180.8 (s, 1C).

Embodiment 8:Cu (MeC (O) CHC (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me) and replaceable synthesis mode

MeC (O) CH with 1.625g (0.0104mol) ₂C (NCH ₂CH ₂NMeH) Me obtains white thickness cream in 0.417g (0.0104mol) potassium hydride KH that is stirring in the dried THF that joins under the nitrogen atmosphere in 100ml 30 minutes time.In 5 minutes time, to the 2.5M n-Butyl Lithium (0.0104mol) that wherein adds 4.2ml, obtain limpid yellow/orange solution.The Chlorodimethyl vinyl silanes (0.01mol) that in solution, adds 1.4ml.Mixture becomes muddy shape at this moment, restir 20 minutes.Then the 5ml that the gained slurry dropwise was added under the nitrogen atmosphere 30 minutes time does among the THF, and wherein this THF is in 0 ℃ and stir 1.04g (0.0104mol) copper (I) muriate is arranged, and then is heated to room temperature and stirs and spend the night.Stripping is removed THF under vacuum, adds 100ml Ganji alkane under nitrogen atmosphere.Filtering mixt, then the stripping hexane obtains crude product, perhaps Cu (MeC (O) CHC (NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃)) Me), this product has obtained evaluation from GCMS.

Claims (3)

1. metal complexes, it is selected from:

Cu (MeC (O) CHC (NCH ₂CH ₂OSiMe ₂(C ₂H ₃)) Me); With

Cu(MeC(O)CHC(NCH ₂CH ₂NMeSiMe ₂(C ₂H ₃))Me)。

2.Cu(MeC(O)CHC(NCH ₂CH ₂OSi?Me ₂(C ₂H ₃))Me)。

3.Cu(MeC(O)CHC(NCH ₂CH ₂NMe?SiMe ₂(C ₂H ₃))Me)。