DE19715786A1 - Silsesquioxane-metal complexes preparation - Google Patents

Abstract

A process for the production of a silsesquioxane-metal complex (I) comprises suspending a metal compound (II) of formula MZxY4-x (1) and a silsesquioxane (III) of formula {(R<1>SiO1.5)n(R<2>SiO1.5)m(H)p(B)q(O)r}(2) in an alkylated hydrocarbon, optionally in the presence of a basic compound at -80-+80 deg C and separating the product at room temperature. In the formulae, M = Group 4-7 metal; Z = halogen or Y; Y = 1-20C alkyl or aryl not containing beta-hydrogen, preferably methyl, benzyl, neopentyl, xylyl, mesityl, neophyl, adamantyl, silyl, fluorenyl, indenyl, cyclopentadienyl, optionally substituted by 1-4C alkyl, 1-4C alkylsilyl, alkoxyaryl or arylsilyl groups, oxo, imido, halogen, or OR (where R =H, 1-20C alkyl, preferably methyl, ethyl, isopropyl, tert-butyl, aryl, preferably benzyl, phenyl, toluyl, naphthyl, xylyl); x = 0-4; R<1> = 5-10C cycloalkyl, norbornyl, optionally substituted with halogen or OH; R<2> = OH; B = SiR<3>y; R<3> = 1-4C alkyl, aryl, SiMe2(CH2)sCH=CH2, SiMe2(CH2)5CH2CH2A, SiMe2(CH2)sCHACH3, optionally substituted by halogen or OH; A = OH, COOH, COOH, NH2, SO3<->, COO;<-> s = 1-20; y = 2 or 3; n = 6 or 7; m = 0 or 1; p = 0-4; and q, r = 0-2.

Description

The invention relates to a method for producing Silasesquioxane metal complexes, new silasesquioxane metal complex as well as their use.

The production of silasesquioxane metal complexes by Implementation of trisilanol, which is substituted with cyclohexyl groups is, with a metal compound is known. (Polyhedron, 1995, Vol. 14, No. 22, pp. 3239-3253).

The production of a trisi containing cyclohexyl groups lanols is very time consuming. However, this is trisilanol very soluble, so that the conversion to the desired Me tall complexes is easily possible.

The preparation of a trisilanol with cyclopentyl is substituted in groups, is possible in a much shorter time Lich. However, the trisilanol is poorly soluble, so that the So far, no production of the corresponding metal complexes has been described.

The previously known methods for producing the Me tall complexes are very time consuming and require large menus solvent, which in turn has to be processed.

The object of the invention is a method ready for the preparation of silasesquioxane metal complexes with which even so far not or only with difficulty  available silasesquioxane metal complexes efficiently for ver can be provided.

The object of the invention is achieved in that the Implementation of the metal compound with a silasesquioxane in a suspension takes place.

According to the invention, a metal compound of the general formula I

MZ _x Y _4-x

in the
M stands for metals of the fourth to seventh subgroup of the PSE, in particular for titanium, zirconium, hafnium, chromium, tungsten, molybdenum, vanadium, niobium, tantalum or rhenium, preferably for titanium or zirconium,
Z for halogen, especially chlorine or Y,
Y for C ₁ -C ₂₀ alkyl or aryl groups which do not contain a beta hydrogen atom, in particular for methyl, benzyl, neopentyl, xylyl, mesityl, neophilic, adamantyl, for silyl, fluorenyl, indenyl, cyclopentadienyl, the individual ligands passing through C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsilyl, alkoxy, aryl or arylsilyl groups can be substituted for oxo, imido, halogen, OR where R is hydrogen, C ₁ -C ₂₀ alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, aryl, in particular benzyl, phenyl, toluyl, naphthyl, xylyl,
where Y can be the same or different and
x mean 0 to 4
and at least one silasesquioxane of the general formula II

{(R ¹ SiO _1.5 ) _n (R ² SiO _1.5 ) _m [(H) _p (B) _q (O) _r ] _y }

in the
R ¹ C ₅ -C ₁₀ cycloalkyl, in particular cyclopentyl, cyclohexyl, cycloheptyl, norbornyl
R ² OH
B SiR _y ³ , where R ^{3 is} C ₁ -C ₄ alkyl, in particular methyl, aryl, in particular phenyl or SiMe ₂ (CH ₂ ) _s CH = CH ₂ , SiMe ₂ (CH ₂ ) _s CH ₂ CH ₂ A, SiMe ₂ (CH ₂ ) _s CHACH ₃ , where A is OH, COOH, NH ₂ , SO ₃ ⁻, COO⁻ and s is 1 to 20,
y represents 2 and 3 and
R ¹ and R ³ can be functionalized by halogen or OH and
n 6 and 7
m 0 and 1
p 0 to 4
q 0 to 2
r 0 to 2
mean,
in an organic solvent, e.g. B. an alkylated aromatic hydrocarbon, preferably toluene, where appropriate in the presence of a basic compound, with stirring at -80 ° C to + 80 ° C and the reaction product is separated at room temperature.

Pyridine is preferably used as the basic compound turns.

By simply centrifuging the by-products severed.  

The silane sesquioxane can be Metal complexes e.g. B. directly by adding acetonitrile falls and cleaned in a known manner z. B. by order crystallization.

The process according to the invention for the preparation of the silesesquioxane metal complexes of the general formula III

{(R ¹ SiO _1.5 ) _n (R ^2a SiO _1.5 ) _m [(B) _q (O) _r ]} _u (M) _v (Y) _w

in the
R ¹ , B, M, Y, n, m, q, r have the meaning given above,
R ^2a oxygen
u 1 to 4
v 1 to 4
w 0 to 12
mean,
is distinguished from the previously known methods by the fact that the solvent requirement can be drastically reduced. The time-consuming refurbishment stages can thus be eliminated.

In one embodiment, compounds of titanium, zircon are preferably used as metal compounds, in particular TiCl ₄ , TiCl ₃ (η ⁵ -C ₅ H ₅ ) or TiCl ₃ {η ⁵ - C ₅ H ₃ (SiMe ₃ 1.3)} or Zr (CH ₂ C ₆ H ₅ ) ₄ used.

In another embodiment, preferably Si lasesquioxane of the general formula II in the

• a) n = 7, m = 1, q = p = r = 0
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃
  R ₂ = OH
• b) n = 7, m = 0, p = q = 1, r = 1.5
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ B = SiR ³ ₂ (where R ^{3 represents} the above-mentioned substituents, in particular methyl or phenyl)
• c) n = 7, m = 0, p = 1, q = 2, r = 1.5
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃
  B = SiR ³ ₃ (where R ^{3 represents} the abovementioned substituents, in particular methyl or phenyl)
• d) n = 7, m = 0, p = 2, q = 1, r = 1.5
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃
  B = SiR ₃ ³ (where R ^{3 represents} the abovementioned substituents, in particular methyl or phenyl)
• e) n = 7, m = q = 0, p = 3, r = 1.5
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃
• f) n = 6, m = q = 0, p = 4, r = 2
  R ¹ = cC ₇ H ₁₃ , norbornyl

mean used.

In particular, silasesquioxanes of the general formula II in which R ^{1 is} cC ₅ H ₉ are used.

In a preferred embodiment, titanium sila sesquioxane complexes made by a titanium compound (I) with a silasesquioxane (II) in an alkylated aroma table hydrocarbon, preferably toluene at 20 to 50 ° C is suspended. With the addition of a basic verb tion, preferably pyridine, the suspension is added keeping a temperature of about 50 ° C stirred. The Wed is cooled to room temperature and the side pro products, preferably separated by centrifugation.  

In another preferred embodiment, a Zirconium compound of the general formula (I) in which x = 0, Suspend with a silasesquioxane (II) in toluene at -80 ° C dated. The mixture is brought to room temperature with stirring warms and the by-products separated in a known manner.

It has been found that the production of this zirconium Silasesquioxane complexes is possible without a basic Compound such as pyridine must be added.

The method according to the invention enables, for example, the production of silasesquioxane metal complexes of the general formula III in which

• 1) n = 7, m = 1, q = r = 0, u = 4, v = 1, w = 0
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  R ^2a = oxygen
  M = Ti, Zr, Hf
• 2) n = 7, m = 0, q = 1, r = 1.5, u = 4
  v = 1, w = 0
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  B = SiR ₂ ³ (where R ^{3 has} the meaning given above)
  M = Ti, Zr, Hf
• 3) n = 7, m = 0, q = 2, r = 1.5, u = 4,
  v = 1, w = 0
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  B = SiR ³ ₃ (where R ^{3 has} the meaning given above)
  M = Ti, Zr, Hf
• 4) n = 7, m = 0, q = 1, r = 1.5
  u = 2, v = 1, w = 0
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  B = SiR _{3 3} (where R ^{3 has} the meaning given above)
  M = Ti, Zr, Hf
• 5) n = 7, m = 0, q = 1, r = 1.5
  u = 2, v = 1, w = 1
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  B = SiR ₃ ³ (where R ^{3 has} the meaning given above)
  M = Cr, Mo, W
  Y = oxo, imido
• 6) n = 7, m = q = 0, r = 15
  u = 1, v = 1, w = 1
  R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  M = Ti, Zr, Hf
  Y = has the abovementioned meaning and is preferably cyclopentadienyl, methyl, benzyl, neopentyl, OH, halogen, alkoxide.
• 7) n = 7, m = q = 0, r = 1.5, u = 1
  v = 1, w = 1 R ¹ = cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , norbornyl
  M = V, Nb, Ta
  Y = oxo, imido
• 8) n = 6, m = q = 0, r = 2, u = 1, v = 1, w = 0
  R ¹ = cC ₇ H ₁₃ , norbornyl
  M = Ti, Zr, Hf
• 9) n = 6, m = q = 0, r = 2,
  u = v = w = 1
  R ¹ = cC ₇ H ₁₃ , norbornyl
  M = Cr, Mo, W
  Y = oxo, imido
• 10) n = 6, m = q = 0, r = 2, u = 1, v = 2,
  w = 4
  R ¹ = cC ₇ H ₁₃ , norbornyl
  M = Cr, Mo, W
  Y = oxo, imido
• 11) 11) n = 6, m = q = 0, r = 2, u = 1
  v = 4, w = 12
  R ¹ = cC ₇ H ₁₃ , norbornyl
  M = Re
  Y = oxo, imido

mean.

The method according to the invention preferably enables the production of silasesquioxane metal complexes, which under Use of cyclopentyl group-containing silasesquioxanes were manufactured.

Such metal complexes have so far been able to poor solubility of the cyclopentyl group-containing sila sesquioxans cannot be manufactured.

The method according to the invention also enables Manufacture of monodentate and multidentate silasesquioxane metal complex. It is also possible to coordinate four-fold To produce metal complexes. The production of silasesqui oxane-polymetal complexes are also possible.  

The metal complexes produced according to the invention are stable, microcrystalline solids.

It was also found that the invention Metal complex produced are particularly suitable as kata analyzer for the oxidation or epoxidation of unsaturated Hydrocarbons, including halogenated alkenes and alcohols.

The use according to the invention of the silasesquioxane Metal complexes as a catalyst is because the active centers in the Metal complex are precisely defined and thus the leaching Behavior can be controlled and controlled as special advantageous compared to the previously known and use to look at the catalysts.

The following examples are intended to explain the invention but not restrict it.

Examples example 1 Preparation of [Ti {η ⁵ -C ₅ H ₃ (SiMe ₃ -1.3)} {(cC ₅ H ₉ ) ₇ Si ₇ O ₁₂ }]

In a suspension of 1.38 g [TiCl ₃ {η ⁵ -C ₅ H ₃ (SiMe ₃ -1.3)}, 3.40 g (cC ₅ H ₉ ) ₇ Si ₇ O ₉ (OH) ₃ and 50 ml of toluene are carried out at 30 ° C 1.5 ml of pyridine with stirring within 15 seconds. The yellowish suspension is heated to 50 ° and cooled to room temperature after 2 minutes. The reaction products or the unreacted starting products are separated by centrifugation. Acetonitrile (175 ml) is added to the clear yellow solution. The metal complex precipitates as a microcrystalline powder.
Yield: 75%

Example 2 Preparation of [(cC ₅ H ₉ ) ₇ Si ₇ O ₁₂ ] ZrCH ₂ C ₆ H ₅

3.05 g of Zr (CH ₂ C ₆ H ₅ ) ₄ are dissolved in 30 ml of toluene and at -80 ° C in a suspension of 5.55 g (cC ₅ H ₉ ) Si ₇ O ₉ (OH) ₃ and 50 ml of toluene introduced. The mixture is warmed to room temperature with stirring and stirring is continued for about 1 hour. The volatile by-products are removed in vacuo and the yellowish product is dissolved in hexane. The insoluble impurities are filtered off.
The solution is concentrated and at -30 ° C. the end product crystallizes out in the form of light yellow crystals.
Yield: 71%

Example 3 Preparation of [(cC ₅ H ₉ ) ₇ Si ₇ O ₁₁ (OSiMe ₃ )] ₂ Ti

In a suspension of 1.03 g (cC ₅ H ₉ ) ₇ Si ₇ O ₉ (OSiMe ₃ ) (OH) ₂ and 0.09 ml TiCl ₄ in 30 ml toluene, 0.22 ml pyridine is added at 20 ° C from 1 min. entered with stirring. The Sus pension is heated to 50 ° C and after 2 min. cooled to room temperature. The mixture is centrifuged. The clear yellow supernatant solution is separated off, mixed with 200 ml of aceto nitrile. The metal complex precipitates as a white, microcrystalline powder.
Yield: 87%

Example 4 Preparation of (cC ₅ H ₉ ) ₇ Si ₇ O ₁₂ V = O

In a suspension of 1.01 g (cC ₅ H ₉ ) ₇ Si ₇ O ₉ (OH) ₃ in 20 ml toluene, 0.29 g (i-PrO) ₃ V = O, dissolved in 2 ml toluene, are dissolved in entered within 15 sec. This mixture is heated to 50 ° C within half a minute and within 30 min. cooled to room temperature. The mixture is then centrifuged and the supernatant solution is separated off. The solution is mixed with 80 ml of acetonitrile. The metal complex precipitates as a white powder.
Yield: 59%.

Example 5 Production of (cC ₇ H ₁₃ ) ₆ Si ₆ O ₁₁ Ti

In a mixture of 0.99 g (cC ₇ H ₁₃ ) ₆ Si ₆ O ₇ (OH) ₄ and 0.12 ml TiCl ₄ in 30 ml toluene, 0.45 ml pyridine are mixed within 1 min. registered. The yellow suspension is in 2 min. heated to 50 ° C and then cooled to room temperature. It is then centrifuged. The supernatant solution is separated off and mixed with 70 ml of acetonitrile. The metal complex precipitates as a white powder.
Yield: 78%.

Claims (7)

1. A process for the preparation of silasesquioxane-metal complexes, characterized in that a metal compound of the general formula I
MZ _x Y _4-x
in the
M metals from subgroup 4 to 7 of the PSE,
Z halogen or Y,
YC ₁ -C ₂₀ alkyl or aryl groups that do not contain beta hydrogen, e.g. B. methyl, benzyl, neopentyl, xylyl, mesityl, neophile, adamantyl, silyl, fluorenyl, indenyl, cyclopentadienyl, the individual substituents being substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl silyl, alkoxy - Aryl or arylsilyl groups can be substituted, oxo, imido, halogen, OR where R is hydrogen, C ₁ -C ₂₀ alkyl, in particular methyl, ethyl, isopropyl, tert. butyl, aryl, especially benzyl, phenyl, toluyl, naphthyl, xylyl
where Y can be the same or different
and x mean 0 to 4
and at least one silasesquioxane of the general formula II
{(R ¹ SiO _1.5 ) _n (R ² SiO _1.5 ) _m [(H) _p (B) _q (O) _r ]}
in the
R ¹ C ₅ -C ₁₀ cycloalkyl, norbornyl
R ² OH
B SiR _y ³ , where R ^{3 can be} C ₁ -C ₄ alkyl, aryl,
SiMe ₂ (CH ₂ ) _s CH = CH ₂ , SiMe ₂ (CH ₂ ) _s CH ₂ CH ₂ A, SiMe ₂ (CH ₂ ) _s CHACH ₃ , where A is OH, COOH, NH ₂ , SO ₃ ⁻, COO ⁻, And s stands for 1 to 20, y stands for 2 and 3 and
R ¹ and R ³ can be functionalized by halogen or OH, and
n 6 and 7
m 0 and 1
p 0 to 4
q 0 to 2
r 0 to 2
mean,
in an alkylated aromatic hydrocarbon, optionally in the presence of a basic compound, with stirring at -80 ° C to + 80 ° C and the reaction product is separated at room temperature. 2. A process for the preparation of silasesquioxane-metal complexes according to claim 1, characterized in that a metal compound of the general formula I in which
M titanium,
Z chlorine,
Y cyclopentadienyl, η ⁵ -C ₅ H ₃ (SiMe ₃ -1.3),
x 3
mean,
and at least one silasesquioxane of the general formula II are suspended in toluene at 20 to 50 ° C. and pyridine is added as the basic compound with stirring and the reaction product is separated off. 3. A process for the preparation of silasesquioxane-metal complexes according to claim 1, characterized in that a metal compound of the general formula I in which
M zircon
Y benzyl
x 0
mean
and at least one silasesquioxane of the general formula II are suspended in toluene at -80 ° C. to -20 ° C. and heated to room temperature with stirring and the reaction product is separated off. 4. A process for the preparation of silasesquioxane-metal complexes according to claim 1, characterized in that a metal compound of the general formula I in which
M titanium,
Z chlorine,
x 4
mean
and at least one silasesquioxane of the general formula II are suspended in toluene at 20 to 50 ° C. and pyridine is introduced as the basic compound with stirring and the reaction product is separated off. 5. A process for the preparation of silasesquioxane-metal complexes according to claim 1, characterized in that a metal compound of the general formula I in which
M vanadium,
Z OR, especially iso-propoxy,
Y oxo,
x 3 mean
and at least one silasesquioxane of the general formula II is suspended in toluene and the reaction product is separated off. 6. Silasesquioxane metal complexes of the general formula III
{(R ¹ SiO _1.5 ) _n (R ^2a SiO _1.5 ) _m [(B) _q (O) _r ]} _u (M) _v (Y) _w
in the
R ¹ , B, M, Y,
n, m, q, r
have the meaning according to claim 1 and
R ^2a oxygen
u 1 to 4
v 1 to 4
w 0 to 12
mean. 7. Use of the silasesquioxane complexes as catalysts Gate for the oxidation or epoxidation of unsaturated carbons hydrogen or alcohol.