JPH0535154B2 - - Google Patents

Description

Claim 1: The production of a group metal alkyl comprising: (a) forming an alkyl adduct; and (b) heating said adduct to cause thermal dissociation, thereby liberating the group metal alkyl as a gaseous product. In this method, the generated adduct has the formula (R ₃ M) _y L. (wherein R ₃ is 3
represents an alkyl group R, R may be the same or different, M represents a group metal element, and L represents
an aryl-containing group donor ligand provided by an organic Lewis base stable at 20° C., y being an integer equal to the number of group donor atoms present in the ligand. 2. The method of claim 1, wherein 2 L is an aryl-containing phosphorus donor ligand. 3. The method of claim 1 or claim 2, wherein the organic Lewis base has a melting point of 50°C to 200°C. 4. The method of claim 1, wherein the heat of formation of the adduct is between 5 and 15 kcal mol ^-1 . 5. The method according to claim 4, wherein the heat of formation of the adduct is 6 to 12 kcal mol ^-1 . 6. The Lewis base for providing the ligand L is selected from aryl-containing group Lewis bases, and each group donor atom present in the base is trivalent and directly bonded to at least one adjacent aryl group. Scope 1 method. 7 Both the organic Lewis base and the ligand L have the general formula 7. The method of claim 6, wherein Ar ¹ and Ar ² are the same or different aryl groups, X is a group atom, and Y is an aryl or aryl-containing group. 8 Both the organic Lewis base and the ligand L have the general formula [In the formula, Ar ¹ , Ar ² and X are as defined in claim 7, and Ar ³ is an aryl group;
May be the same or different from one or both of Ar ¹ and Ar ² , and Z is

[Formula] (In the formula, D is an aromatic or aliphatic group, and Ar ⁴
is an aryl group) and n is an integer from 1 to 5. 9. The method of claim 8, wherein ^Ar1 , ^Ar2 , ^Ar3 and ^Ar4 are independently selected from phenyl, substituted phenyl, p-diphenyl and naphthyl. 10. The method of claim 9, wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each phenyl. 11. Claim 8, wherein D is an aliphatic chain having the formula (CH ₂ ) _n , where m is an integer from 1 to 12.
the method of. 12. The method of claim 11, wherein 12 m is from 2 to 4. 13. The method of claim 8, wherein n is 1 to 3. Description The present invention relates to the production of metal alkyls useful in the production of compound semiconductor materials. Compound semiconductor materials, such as gallium arsenide, indium phosphide, gallium phosphide, and cadmium mercury telluride, have applications in the electronics industry, such as in microwave resonators, semiconductor light-emitting diodes and lasers, and infrared detectors. It is a well-known material. Such materials are conventionally manufactured by forming one or more active layers on a substrate crystal, usually by vapor phase epitaxy (VPE). It has been known for some time that compound semiconductors of the form MQ, where M is a group element and Q is a group element, can be produced by VPE by reacting a trialkylated product of element M with a gaseous compound of group element Q, such as a hydride. known from. This method is suitable, for example, for producing gallium arsenide (gallium arsenide) from Ga(CH ₃ ) ₃ and AsH ₃ . For this reason, metal alkyls, especially group trialkyl compounds such as trimethylgallium and trimethylindium, have become important in the production of semiconductor materials. However, metal alkyls such as trimethylgallium and trimethylindium are extremely dangerous because they are volatile, pyrophoric, and have explosively high hydrolysis reactivity. Trimethylgallium and trimethylindium require special containers, which are extremely expensive to prepare. Electronics Letters
Letters), March 13, 1980, Vol. 16, No. 6, by H.Renz and J. Weidlein describes the adduct of trimethylindium and the Lewis base P(CH ₃ ) ₃ . Generation is described. The adduct thus produced is solid at room temperature and can be safely purified by zone purification. However, it is difficult to separate trimethylindium from the adduct described in this document. It is an object of the present invention to provide a metal alkyl adduct which is stable at room temperature and, when necessary, easily separated into its components above a fairly low thermal decomposition (dissociation) temperature. An object of the present invention is to provide a method for producing alkyl. The method for producing a group metal alkyl provided by the first aspect of the present invention includes (a) formula (R ₃ M) _y ·L [wherein R ₃ is three alkyl groups which may be the same or different]; represents a group R, M represents a group metal element,
L represents an aryl-containing group donor ligand provided by an organic Lewis base stable at 20°C, and y is an integer equal to the number of group donor atoms present in the ligand. , (b) heating the adduct to cause its thermal dissociation, thereby liberating the metal alkyl as a gaseous product. L is preferably an aryl-containing phosphorus donor ligand. The process is particularly suitable for the production of lower alkylated group metals, in particular hexamethyldialuminium, trimethylgallium and trimethylindium. Lewis bases suitable for providing the ligand L are aryl-containing group Lewis bases, in particular those in which the group donor atom(s) present in the base are trivalent and bond directly to at least one adjacent aryl group. It is something that The main advantages of using aryl instead of alkyl Lewis bases are: The basicity of this Lewis base is reduced, so the dissociation temperature of the adduct formed from it is lower. The volatility of this Lewis base is generally low. Because of these two advantages, the adducts formed in the process of the present invention readily dissociate at relatively low temperatures to produce gaseous alkyl products containing only low concentrations of contaminating Lewis bases. Aryl-containing group Lewis bases that have been found to have acceptably low volatility for the purposes of this invention are those with melting points in the range of 50°C to 200°C. Furthermore, preference has been found to be given to Lewis bases which give adducts of the formula (R ₃ M) _y.L with a heat of formation of 5 to 15 kcal mol ^-1 , especially 6 to 12 kcal mol ^-1 . Adducts with a heat of formation of less than about 5 kcal mol ^-1 are not suitable for this method because they tend to dissociate at room temperature (15-20 °C), and adducts with a heat of formation of less than 12 kcal
Adducts larger than mol ^-1 and especially larger than 15 kcal mol ^-1 usually require unacceptably high dissociation temperatures, which can result in high levels of contaminant Lewis bases in the gaseous alkyl product. . It is preferred that both the ligand L and the organic Lewis base from which it is derived have the general formula. Moreover, it is most preferable to have the following general formula. However, Ar ¹ , Ar ² and Ar ³ are the same or different aryl groups, X is a group atom, and Y
is an aryl group or an aryl-containing group, and Z is

[Formula] (where D is an aromatic or aliphatic group and Ar ⁴ is an aryl group), and n is an integer from 1 to 5. X is preferably phosphorus. Ar ¹ , Ar ² and (in the formulas) Ar ³ and Ar ⁴ each represent phenyl, substituted phenyl (e.g. o-, p-, or m-tolyl C ₆ H ₄ CH ₃ or mesityl C ₆ H ₂
( _CH3 ) ₃ ), p-diphenyl or naphthyl. The groups Ar ¹ , Ar ² , Ar ³ and
Preferably Ar ⁴ is phenyl. D is an aliphatic chain (CH ₂ ) _n (where m is 1 to
is an integer of 12, most preferably 2 to 4), and n is preferably 1 to 3. Examples of the monodentate ligand L of the general formula are triphenylphosphine, tris-p-toylphosphine, trimesitylphosphine, tris-p-
Biphenylphosphine and trinaphthylphosphine are examples of bidentate and polydentate ligands L of the general formula DIPHOS.
(Ph ₂ PCH ₂ CH ₂ PPh ₂ ), TRIPHOS
(Ph ₂ PCH ₂ CH ₂ P(Ph)CH ₂ CH ₂ PPh ₂ ) and
TETRAPHOS−1 (Ph ₂ PCH ₂ CH ₂ P (Ph)
CH ₂ CH ₂ P (Ph) CH ₂ CH ₂ PPh ₂ ) (Ph = phenyl)
There is. One particular advantage of using bidentate and especially polydentate Lewis bases of the general formula instead of monodentate Lewis bases of the general formula is that the latter has a lower thermal dissociation temperature than the melting point of the base. The formula with (R ₃ M)
It can be seen that adducts of _y ·L are easily formed. The rate of alkyl liberation from a solid base/adduct mixture depends only on temperature and is largely independent of the concentrations of adduct and Lewis base dissociation products, which vary as dissociation proceeds. The inventors have found that a further advantage of using Lewis bases of the general formula when X is phosphorus, especially when using Lewis bases of the general formula, is that they readily form adducts with the normal group metals. I discovered that what you should do is not do it. The presence of even trace amounts of group metals can interfere with the VPE growth of group/group compound semiconductor layers and can act as unwanted dopants within these layers. Therefore, the use of these aryl-containing phosphorus Lewis bases in the present process provides an additional method for purifying group metal alkyls. This is because the (R ₃ M) _y ·L adducts produced by this method generally do not contain group metal impurities. To produce the adduct (R ₃ M) _y・L, use the formula
Preferably, a precursor adduct of R ₃ M.E (E is an ether) is formed and a substitution reaction takes place between this precursor adduct R ₃ M.E and the group donor ligand L. Although L may be weaker than E as a Lewis base, it is possible to balance the substitution reaction by distilling off the volatile ether E so that the desired (R ₃ M) _y ·L adduct is formed. It can be shifted. For example, E can be diethyl ether,
PAr ₃ can be replaced especially with triphenylphosphine etc. as specified above or with DIPHOS, TRIPHOS or TETRAPHOS. 1
For example, when producing (CH ₃ ) ₃ Ga.(C ₂ H ₅ ) ₂ O, a reaction heat of approximately 20 kcal mol ^-1 (84 kJ mol ^-1 ) is generated, whereas the weaker Lewis base
The reaction heat generated during the production of (CH ₃ ) ₃ Ga・PPh 3 containing PPh ₃ is approximately 6 kcal mol ^-1 (25 kJ _mol ^-1 )
Only. The reaction heat during formation is approximately 5 kcal mol ^-1
(21 kJ mol ^-1 ) is unsuitable as an adduct of the present invention because it tends to dissociate at room temperature. Precursor adducts of formula R ₃ M.E can be prepared by one of many known routes. For example, when R ₃ M is (CH ₃ ) ₃ Ga or (CH ₃ ) ₃ In, ether E is present in the form of a solvent and GaCl ₃
Alternatively, InCl ₃ may be reacted with either CH ₃ Li or a suitable Grignard reagent. According to the second aspect of the present invention, the general formula (R ₃ M) _y・
An adduct of L is provided. Here, R ₃ represents three alkyl groups R that may be the same or different,
M represents a group metal element, L represents an aryl-containing group donor ligand derived from an organic Lewis base stable at 20° C., and y is an integer equal to the number of group donor atoms present in this ligand.
Preferably L represents a phosphorus donor ligand;
Preferably M represents aluminum, gallium or indium. Each R preferably represents a lower alkyl group, with methyl being most preferred. The Lewis base that forms the origin of ligand L is
Low volatility solids that melt in the range 50°C to 200°C are preferred. The heat of formation of adduct (R ₃ M) _y・L is 5 to 15 kcal
mol ^-1 and most preferably 6 to 12 kcal mol ^-1 . L is conveniently derived from a Lewis base in which the group donor atom(s) present in the base are trivalent and bond directly to at least one adjacent aryl group. L preferably has the following general formula, The following general formula is most preferred. Here, Ar ¹ , Ar ² and Ar ³ are the same or different aryl groups, X is a group V atom, and Y
is an aryl group or an aryl-containing group, and Z is

[Formula] (where D is an aromatic or aliphatic group and Ar ⁴ is an aryl group), and n
is an integer from 1 to 5. X is preferably phosphorus. Ar ¹ , Ar ² and (in the formula) Ar ³ and Ar ⁴ each represent phenyl, substituted phenyl (e.g. o-, p-
or m-tolyl C ₆ H ₄ CH ₃ , or mesityl
_C6H2 ( _{CH3 ) 3} ), p-diphenyl or naphthyl. Preferably, the radicals Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are phenyl. D is preferably an aliphatic chain (CH ₂ ) _n (where m is an integer of 1 to 12, most preferably 2 to 4), and n is preferably 1 to 3. Examples of monodentate ligands L of general formula I include triphenylphosphine, tris-p-toylphosphine, trimesitylphosphine, tris-p-
Biphenylphosphine and trinaphthylphosphine are examples of bidentate and polydentate ligands L of the general formula DIPHOS.
(Ph ₂ PCH ₂ CH ₂ PPh ₂ ), TRIPHOS
(Ph ₂ PCH ₂ CH ₂ P(Ph)CH ₂ CH ₂ PPh ₂ ) and
TETRAPHOS−1 (Ph ₂ PCH ₂ CH ₂ P (Ph)
CH ₂ CH ₂ P (Ph) CH ₂ CH ₂ PPh ₂ ). By producing metal alkyls in the method of the first aspect of the invention, it is possible to avoid the difficulties mentioned above regarding the production, transport and handling of volatile metal alkyls. However, in order to make the metal alkyl available at the point of use (e.g. in a VPE device), it is necessary to prepare the adduct at a relatively low temperature, e.g. in an inert gas at atmospheric pressure or under reduced pressure ( _{R 3} M). The metal alkyl may be separated from this adduct by heating to . For example, (CH ₃ ) ₃ Ga PPh ₃ is heated at 180°C in nitrogen at atmospheric pressure.
Alternatively, trimethylgallium can be obtained from this adduct by heating to 90°C under reduced pressure (10 ^-2 mmHg). Formula (R ₃ M) which is a specific example of the second aspect of the present invention
The adducts of _y ·L are preferred for use in processes for the production of semiconductor compounds over known adducts containing ligands such as (CH ₃ ) ₃ P and adducts containing ethers and other oxygen-containing ligands. . This is because the ligand L can be easily separated from the alkylated product, and the trace amount of the ligand L is unlikely to act as a dopant in the produced semiconductor compound. DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the present invention will be described below with reference to the accompanying drawings. In the figure, FIG. 1 is a graph of intensity versus atomic mass of the mass spectrum of the product of reaction 2 specified below. FIG. 2 is a graph of infrared transmittance versus wave number of the infrared absorption spectrum of the product of reaction 2 specified below. The following symbols are used in the examples below. mp = melting point bp = boiling point NMR = nuclear magnetic resonance spectrum IR = infrared ppm = parts per million Example 1 Precursor adduct Me ₃ Ga・Et ₂ O (Et = ethyl) to adduct Me ₃ Ga・PPh ₃ Trimethylgallium Me ₃ Ga was prepared from this adduct by obtaining:
This precursor adduct was obtained from methyllithium in diethyl ether. The overall reaction route used is as follows. GaCl ₃ ＋3MeLiEt ₂ O −−→ Me ₃ Ga・Et ₂ O＋3LiCl ……Reaction 1 Me ₃ Ga・Et ₂ O＋PPh ₃ →Me ₃ Ga・PPh ₃ ＋Et ₂ O
...Reaction 2 Me ₃ Ga・PPh ₃ → Me ₃ Ga + PPh ₃ ...Reaction 3 1.1 Production of trimethyl gallium etherate: Reaction 1 Add methyllithium (112 ml of 1.67M solution) in ether to GaCl ₃ (ether) while stirring on ice.
11.0g in 50ml). The mixture was stirred overnight at room temperature, filtered, and the liquid was
All the solvent is removed using a Vigreux column (length 16 cm) and Me ₃ Ga Et ₂ O is distilled out (bp 99°C).
It was fractionated to The yield was 10.3g (87%). 1.2 Preparation of the adduct Me ₃ Ga PPh ₃ : Reaction 2 Triphenylphosphine (3.6 g) in benzene (30 ml) is dissolved in benzene (10 ml) at room temperature.
Me ₃ Ga·Et ₂ O, 92.6 g). This mixture was applied to a Vigreux column (16 cm long).
The temperature of the distillate was 80℃ (benzene).
The low boiling fraction (36°C) was removed until reaching bp). The mixture was then cooled and concentrated to the crystallization point by evaporating the solvent under reduced pressure. 1.7 g of crystalline compound was obtained. This was recrystallized from pentane (approximately 120 ml) until the melting point was constant. This compound melts at 132°C without significant decomposition. The structure of this adduct was confirmed by IR, NMR, and mass spectra. The samples were also subjected to microanalysis (C and H). The measured values were C, 66.6%, and H, 6.47%. Me ₃ Ga・
PPh ₃ is C, 66.9%, H, 6.41%. The obtained IR, NMR and mass spectrum results are as follows. ¹ HNMR (in C ₆ D ₆ ) PPh ₃ Hydrogen atom in phenyl group (δ, 8.25−
The molar ratio of Me ₃ Ga (6.90 ppm) to the hydrogen atoms (0.2 ppm) in the methyl group was 1.8:1 (calculated value: 1.66:1) according to NMR peak integration. The reason why the obtained value is somewhat large is explained by the influence of the molecular species C ₆ H _x D _6-x (x = 1 to 6) present in trace amounts in the C ₆ D ₆ solvent, which contributes to the peak intensity of phenyl. Ru. Mass spectrum (70eV) The results are shown in Figure 1. No parent ion of the adduct was observed. Appearing peaks: PPh ₃ ⁺ mass 262.3 Me ₃ Ga ⁺ mass 116.2 and 114.2, ( ⁷¹ Ga and ⁶⁹ Ga
by isotope) Me ₃ Ga ⁺ masses 101.2 and 99.3 MeGa ⁺ masses 86.2 and 84.1 Ga ⁺ masses 71.1 and 69.1 The intensity ratio of gallium for the two isotopes (71 and 69) of gallium-containing species is about 1.5, which Natural abundance ratio of isotopes Ga ⁶⁹ −60.4%, Ga ⁷¹ −
It is in good agreement with 39.6%. IR spectrum The obtained spectrum is shown in Figure 2. This reconfirms the structure of the adduct. 1.3 Production of Me ₃ Ga: Reaction 3 The production of Me ₃ Ga and PPh ₃ was repeated twice. The purpose is to remove the adduct by heating action using an oil bath under 1 atmospheric pressure and 2 under reduced pressure.
This is to separate it into Me ₃ Ga and PPh ₃ . In all cases an excess (approximately 20%) of PPh ₃ was used. The adduct was obtained as in 1.2 above. However, instead of the final crystallization with benzene, the solvent was evaporated under reduced pressure and the product was used without further purification. The sample heated under nitrogen was Me ₃ Ga at 180 °C.
The gas that was identified as Heating was stopped at this point. Samples heated under reduced pressure (10 ^-2 mmHg) began to evolve Me ₃ Ga at approximately 80°C (oil bath temperature). At this temperature the solid in the flask started to melt (mp for PPh ₃ = 80 °C). Heating was continued and the temperature was slowly raised to 90°C. Heating was stopped approximately 15 minutes after all of the contents of the flask had melted and no gas evolution was visible. Me ₃ Ga was collected in a liquid nitrogen trap. Me ₃ Ga has an NMR spectrum (δ, −
0.07ppm; C ₆ D ₆ ). Me ₃ Ga is 1.3g
recovered, yield based on Me ₃ Ga Et ₂ O is 71%
It was hot. (The production started from 3 g of Me ₃ Ga.Et ₂ O.) The residue remaining in the flask after heating was examined by NMR. According to it, the amount of methylgallium species in the form of adducts is negligible and the total
PPh ₃ , which could therefore be reused in this process. Example 2 Adduct (Me ₃ In) Production of Me ₃ In from ₂ -DIPHOS (DIPHOS=Ph ₂ P−CH ₂ −CH ₂ −PPh ₂ , Ph=
phenyl). Step 2a: Preparation of adduct (Me ₃ In) ₂ , DIPHOS A 1.3M methyllithium solution in ether (65 ml) was added to InCl ₃ (6 g) in ether (50 ml). The mixture was refluxed for 2 hours. Benzene (100ml) was added to this solution by a solution of DIPHOS (6g) in benzene (100ml). Ether was removed by fractional distillation on a Vigreux column. The remaining benzene solution was filtered and the solvent was evaporated under reduced pressure. The crude compound (9.78 g) with a mp of 156°C was purified by repeated crystallization from benzene until the melting point was constant (163°C). The properties of this compound were examined by IR, NMR/mass spectroscopy, and elemental analysis. The results are as follows. NMR. ¹ H chemical shift (ppm) In( _{CH3 ) 3} : 0.07; DIPHOS: _CH2 : 2.50 (double line) _C6H5 : 7.52−7.27 and 7.07−6.9; integration gives _CH3 : _CH2 ratio As expected, the ratio was 4.5:1. Elemental analysis: Measured value: C, 53.83; H, 5.90% (Me ₃ In) Calculated value for ₂・DIPHOS: C, 53.51; H, 5.89% Mass spectrum mass intensity DIPHOS ⁺ 397.8 1.4% In ¹¹⁵ Me ₂ ⁺ 144.9 100 In ¹¹³ Me ₂ ⁺ 143.0 4.7 In ¹¹⁵ Me ⁺ 130.0 12.2 In ¹¹³ Me ⁺ 128.0 1.3 Step 2b: Preparation of Me ₃ In (Me ₃ In) ₂ from DIPHOS adduct Connected to a glass container immersed in liquid nitrogen and vacuum Under reduced pressure (10 ^-2 mmHg) in a flask connected to a pump
(Me ₃ In) _2.DIPHOS (3.07 g) was heated in the solution.
Heating (oil bath) was gradually increased. at almost 80℃
Me ₃ In began to be collected in a glass container. 120℃
The decomposition reaction became intense and the contents of the reaction flask became pale brown and foamy. Keep the temperature relaxed
The temperature was raised to 130°C and kept constant until foaming completely stopped. The white compound (1.01 g) collected in the glass container was identified by NMR as Me ₃ In (one peak at 0.2 ppm). Yield 87%. In the NMR spectrum of the residue left in the reaction flask,
There was only the peak of DIPHOS. Example 3 Production of Me ₃ Ga from adduct (Me ₃ Ga) ₂ -DIPHOS Step 3a: Production of adduct (Me ₃ Ga) ₂ -DIPHOS GaCl ₃ and
Me ₃ Ga·Et ₂ O was produced from MeLi and distilled before use. DIPHOS (8.2g) in benzene (150ml)
A solution of Me ₃ Ga Et ₂ O (6.8
g) and the mixture was stirred at room temperature for half an hour. The volatile ether was then removed by fractional distillation (Vigreux column) and the benzene was evaporated under reduced pressure. mp.155℃ crude compound (12.5
g) was purified by repeated crystallization with benzene until the melting point became constant (163°C). The properties of this compound were examined by NMR, IR, mass spectrometry and elemental analysis. NMR. ¹ H chemical shift (ppm) Ga(CH ₃ ) ₃ : 0.15; DIPHOS: CH ₂ , 2.52;
C ₆ H ₅ 7.55-7.27 and 7.1-6.87 Elemental analysis Observed value: C, 61.39; H, 6.73% (Me ₃ Ga) Calculated value as 2.DIPHOS: C, 61.20; _H , 6.74% Step 3b (Me ₃ Ga) from ₂・DIPHOS adduct
Production of Me ₃ Ga (Me ₃ Ga) ₂ .
DIPHOS (3.32 g) was heated under reduced pressure (10 ^-2 mmHg). The temperature of the oil bath was slowly raised to 130°C.
Generation of Me ₃ Ga started at about 80℃ and became intense at 110℃. The recovered dry Me ₃ Ga was distilled again at room temperature under reduced pressure and identified by NMR (one peak at 0.12 ppm). Yield 1.01g (91.2%). The NMR spectrum of the residue in the reaction flask showed only a "DIPHOS" peak. Example 4 Preparation of (CH ₃ ) ₆ Al ₂ from adduct (Me ₃ Al) ₂ DIPHOS Step 4a: Preparation of adduct (Me ₃ Al) ₂ DIPHOS (1.15M) Me ₆ Al ₂ in hexane "Trimethylaluminum" in the form of 21 ml of solution was added to DIPHOS (10.2 g) dissolved in benzene (250 ml).
Approximately 50 ml of volatile material was distilled off using a fractionating column and the remaining solution was concentrated to 50 ml under reduced pressure. A white solid was deposited. I passed this. Yield 9.2g
(62%), MP.~163℃. NMR. ^1H chemical shift (ppm) Al(CH ₃ ) ₃ : −0.175; DIPHOS, CH ₂ : 2.62,
_{C6H5 :} 6.87-7.12 and 7.32-7.61. Integration: CH ₃ :CH ₂ =4.5:1 Mass spectrum DIPHOS ⁺ (m/z, 398.4, 68.1%) and Me ₂ Al ⁺
A main peak of (m/z, 57.3, 100%) was observed. Step 4b: Preparation of Me ₆ Al ₂ from (Me ₃ Al) ₂ DIPHOS adduct Heat DIPHOS (3.0 g) with (Me ₃ Al) under reduced pressure and cold trap the volatile Me ₆ Al _2. (liquid
_N2 temperature). Dissociation began at approximately 115°C (heating bath temperature). The substance melted at 140°C and bubbling was observed. Heating was continued until bubbling ceased.
Yield 0.71g (87.6%). This product has a ¹ H NMR spectrum (δ, −
0.35ppm), it was identified as Me ₆ Al ₂ . Example 5 Production of Mn _{3 In from adduct (Me 3 In} ) _3.TRIPHOS Step 5a _: Production of adduct (Me ₃ In) 3.TRIPHOS Dissolve TRIPHOS (1.5 g) in benzene (20 ml), ₃ In (1.3 g) was condensed and added at liquid nitrogen temperature under reduced pressure. After warming to room temperature, the solvent was evaporated under reduced pressure, leaving an oil (2.8 g). ^NMR.1H chemical shift (ppm) In( _CH3 ) ₃ : 0.125; TRIPHOS, _CH2 : 1.90−
2.60, _{C6H5 :} 6.9−7.17 and 7.27−7.67. Integration: CH ₃ :CH ₂ = 3.10:1 Mass spectrum Main peak is m/z 540 (TRIPHOS), 145/143
(Me ₂ In) and 130/128 (MeIn). Step 5b: Preparation of Me ₃ In from (Me ₃ In) ₃・TRIPHOS adduct (Me ₃ In) ₃・TRIPHOS (2.8 g) was heated under reduced pressure and Me ₃ In was cooled to the temperature of liquid nitrogen. It was condensed and collected. Me ₃ In started to be liberated from the adduct when the temperature reached 60°C in the heating bath, and it became rapid at 75°C. Slowly raise the temperature to 145℃ and add a certain amount of
Me ₃ In (1.0 g, 75.7% yield) was recovered over 3 hours and identified by ¹ HNMR. NMR of non-volatile residues
The spectrum shows that TRIPHOS is coordinated
It was confirmed that a small amount of Me ₃ In was included. Example 6 Adduct (Me ₃ Al) from ₄・TETRAPHOS
Production of Me ₆ Al ₂ Step 6a: Adduct (Me ₃ Al) ₄ .
Manufacture of TETRAPHOS TETRAPHOS (2.55g) is mixed with benzene (100ml)
To this was added Me ₆ Al ₂ (Me ₆ Al ₂ 1.15M) in the form of a hexane solution (6.6 ml). next
TETRAPHOS was dissolved by reacting with Me ₆ Al ₂ to form a soluble adduct. Hexane and other volatile impurities were removed by fractional distillation, and the benzene was evaporated under reduced pressure at room temperature, leaving a white solid adduct (3.92 g). NMR・^1H chemical shift (ppm) Al(CH ₃ ) ₃ : −0.25; TETRAPHOS, CH ₂ :
1.85 − 2.62, C ₆ H ₅ : 6.87 − 7.15 _and 7.30 − 7.75 Integral: CH ₃ : CH ₂ = 3:1 Step 6b: Preparation of Me ₆ Al ₂ from (Me ₃ Al) 4.TETRAPHOS adduct (Me ₃ Al) _4.TETRAPHOS (1.58 g) was heated under reduced pressure and condensed in a liquid nitride cold trap to recover Me ₆ Al. The release of Me ₆ Al ₂ occurs when the bath temperature is 60
This was seen when the temperature reached ℃. Relax the temperature 140
Raised to ℃. The yield of Me ₆ Al ₂ (0.48 g) was quantitative.