JP4402482B2 - Transition metal complex of calixarene compound and adsorbing material comprising the same - Google Patents

Description

  The present invention relates to a calixarene compound in which a group having a phosphorus atom alternately introduced into a hydroxyl group of a phenyl group of calixarene, more specifically a calix [6-12] arene compound represented by the general formula (I), The transition metal complex relates to an adsorbing material using the same.

Calixarene is a compound named by combining calix meaning the Greek cup and the aromatic aryl, and a cyclic compound produced from a phenol derivative and formaldehyde in the presence of concentrated alkali. It is. A polymer of phenol and formaldehyde is known as a phenol resin, but the cyclization reaction is preferred under concentrated alkaline conditions, and calixarene is usually produced in a yield of 40 to 80%. Most of them are 4 to 8 mers, but it has been reported that up to 12 mers can be produced depending on conditions (see Non-Patent Documents 1, 2 and 3). The calixarene n-mer is named calix [n] arene.
The calixarene has a structure in which a phenol derivative is condensed at the ortho position of the phenolic hydroxyl group to form a ring, and has a shape like a cup. The hydroxyl side of the ring is called the lower end, and the para position of the hydroxyl group is called the upper end. Calixarene is a cyclic compound having an oxygen atom and has a similar function to a crown ether or the like, and is expected to function as a sodium ion sensor or an adsorbing material.

Many compounds have been reported in which a phosphorus atom is introduced at the lower end of calixarene, but relatively few examples have introduced a phosphorus atom, particularly phosphine, at the upper end. This is because it is relatively easy to introduce a phosphorus atom into a hydroxyl group, but it is relatively difficult to introduce a phosphorus atom directly bonded to the phenyl ring.
The present inventors have produced a methyl ether of calix [4] arene in which phosphine is introduced at the para position on the upper end side, and have reported the configuration thereof. In this calix [4] arene, as shown by the following formula,

Cone type with the tops all pointing in the same direction (cone), partial cone type with one phenyl group facing in the opposite direction, two phenyl groups facing each other in the opposite direction 1,3- There were four types of three-dimensional structures, alternating (1,3-alternate) and 1,2-alternate with two adjacent phenyl groups facing in the opposite direction (non-native). (See Patent Document 4).
Furthermore, the present inventors produce a benzyl ether derivative of a compound in which a phosphine at the para position of two phenyl groups facing each other of calix [4] arene is introduced and react this with platinum or palladium, for example, PdCl. ₂ (cod) (wherein cod represents 1,5-cyclooctadiene),

The metal complex of the calixarene represented by these has been manufactured (refer nonpatent literature 5).

Boehmer, V., (1995) Angew. Chem. Int. Ed. Engl., 34, 713 Shinkai, S., (1993) Tetrahedron, 49, 8933 Gutsche, C. D., et al., (1998); In Monographs in Supramolecular Chemistry, Royal Society of Chemistry, U. K .; K. Takenaka, Y. Obora, et al., (2001) Bull. Chem. Soc. Jpn., 74, 1709. K. Takenaka, Y. Obora, et al., (2002) Organometallics, 21, 1158.

Thus, the metal complexes of calixarenes have nano-controlled spaces with supramolecular interaction ability, and are provided with functions such as advanced molecular recognition and substrate selection ability that could not be achieved conventionally. Expected to be used as a molecular catalyst based on periodic molecular size control, the present inventors can easily construct a ring structure having an arbitrary size, and a calixarene site having a vacancy showing a host function in the molecule Has been developed, and so far, synthesis of upper rim (upper end) modified calix [4] arene phosphorus ligand (1,2) and complexation behavior with palladium and platinum complexes have been studied (See Non-Patent Documents 4 and 5).
The present invention provides a novel calixarene compound and a metal complex thereof. The calixarene metal complex of the present invention has a capsule structure and is useful as a molecular sieve or an adsorbing material, and the present invention also provides such a use.

  The present inventors have synthesized new cyclic metal compounds aiming at synthesis of metal compounds having functions such as molecular recognition for organic compounds. As a result, the metal complex of calixarene in which phosphorus atoms are alternately introduced into the phenyl ring of calixarene, particularly calix [6] arene, 1,1,2,2-tetrachloroethane, benzene, toluene, o- As a result, xylene and m-xylene could be taken into the pores, and molecules such as naphthalene, cumene and p-xylene were not taken into the pores. As a result, it was found that the nano-controlled space formed by calixarene can be used as a nano-scale molecular control field capable of size-recognizing molecules.

  That is, the present invention relates to the general formula (I)

Wherein R ¹ represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, and R ² and R ³ each independently represents a hydrogen atom, a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, X is C represents an alkylene group of _{1 to 10} , Y represents an aryl group or an aryloxy group, and n represents an integer of 3 to 6.)
And a calixarene compound in which phosphorus atoms are alternately introduced.
The present invention also relates to a transition metal complex of calixarene obtained by reacting the calixarene compound of the present invention with a transition metal compound, more specifically, a transition metal complex of calixarene, which is represented by the following general formula (II): )

Wherein R ¹ represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, and R ² and R ³ each independently represents a hydrogen atom, a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, X is C represents an alkylene group of _{1 to 10} , Y represents an aryl group or an aryloxy group, M represents a transition metal atom, Z represents an anion group, and m represents a value corresponding to the valence of the transition metal M. And n represents an integer of 3 to 6.)
It is related with the transition metal complex of calixarene represented by these.
The present invention also relates to a method for producing a transition metal complex of a corresponding calixarene compound by reacting the calixarene compound of the present invention described above with a transition metal compound in a solvent.
Furthermore, the present invention relates to an adsorbing material comprising a transition metal complex of the calixarene compound of the present invention described above.

The substituent in the calixarene compound represented by the general formula (I) in the present invention will be described.
As an alkyl group in this invention, C1-C20, Preferably it is 1-15, or a C1-C10 linear or branched alkyl group is mentioned. Preferred alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl. Examples include groups.
As an alkylene group in this invention, a C1-C10, Preferably a C1-C5 linear or branched alkylene group is mentioned. Preferred alkylene groups include methylene group, ethylene group, propylene group, butylene group, 2-methylpropylene group and the like.
Examples of the cycloalkyl group in the present invention include a monocyclic, polycyclic, condensed cyclic, or bridged cyclic alkyl group having 3 to 20, preferably 5 to 15 or 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a bicyclo [2,2,1] heptyl group.
As the cycloalkyl-alkyl group in the present invention, the total number of carbon atoms is 4 to 20, preferably 6 to 15, or the number of carbon atoms is 6 to 10, and the above-described alkyl group is bonded to the above-described cycloalkyl group. Groups. For example, a cyclopentyl-methyl group, a cyclopentyl-ethyl group, a cyclohexyl-methyl group, a cyclohexyl-ethyl group, a bicyclo [2,2,1] heptyl-methyl group and the like can be mentioned.

As the aryl group in the present invention, a monocyclic, polycyclic, or condensed cyclic carbocyclic aromatic group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, or a heterocyclic group. An aromatic group is mentioned. In the case of a heterocyclic ring, a ring having 1 to 3 hetero atoms each independently selected from a nitrogen atom, an oxygen atom, or a sulfur atom is included. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, and a pyridyl group, and a preferable aryl group includes a phenyl group.
The aryloxy group in the present invention is a group in which an oxygen atom is bonded to the above-described aryl group, and examples thereof include a phenoxy group and a naphthyloxy group.
The aralkyl group in the present invention is a straight-chain or branched aralkyl group having 7 to 20, preferably 7 to 15 or 7 to 10 carbon atoms, and includes the above-described alkyl group of the present invention. The above aryl group is bonded. Examples of the aralkyl group include a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.
Various substituents that do not inhibit the activity of the molecular sieve of the present invention may be bonded to the alkyl group, aryl group, cycloalkyl group, cycloalkyl-alkyl group, and aralkyl group described above of the present invention. . Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen such as chlorine and bromine, an amino group substituted with an alkyl group having 1 to 20 carbon atoms, and nitro. Group, cyano group and the like.

Examples of the transition metal M in the present invention include metal elements belonging to groups Ib to VIIb and VIII of the periodic table. Examples thereof include rhodium, iridium, palladium, platinum, ruthenium, nickel, and cobalt. Preferred transition metals include rhodium and iridium.
The valence (oxidation number) of these transition metals may be any of 0 valence, 1 valence, 2 valence, or 3 valence, but it must be valence capable of forming a complex with a phosphorus atom.
The anion in the present invention is not particularly limited as long as it is an anion that can exist stably with the transition metal having the oxidation number described above. Examples of the anions include halogen ions such as chlorine ions and bromine ions, nitrate ions, sulfate ions, boron halide ions such as tetrafluoroboron ions, and perhalogenate ions such as perchlorate ions. Etc.
M in the general formula (II) of the present invention is the number of the above-mentioned anions, and this value is a value corresponding to the valence of the transition metal, and is any one of 0, 1, 2, 3 and the like. .

In the general formula (I) of the present invention, R ² and R ³ may be in any position (excluding the ortho position) with respect to the oxygen atom bonded to the phenyl ring, and substituted with two or more groups. Preferably, one in which R ² and R ³ are each in the para position may be mentioned. In addition, R ² and R ³ may be different groups, but are preferably the same group for ease of production.
R ¹ in the general formula (I) of the present invention may be a hydrogen atom, preferably a group other than a hydrogen atom.
In the general formula (I) of the present invention, the two Y bonded to the phosphorus atom are preferably the same kind of group, but are not necessarily the same kind of group. Y may be an aryl group or an aryloxy group. When Y is an aryloxy group, Y may be a phosphite having an oxygen atom inserted between the group X and a phosphorus atom. Good.

The calixarene compound represented by the general formula (I) of the present invention can be produced by the following method. First, according to the method described in the literature, a substituted phenol and formaldehyde are reacted in the presence of concentrated alkali to produce a substituted calixarene compound. Then, according to the method described in the literature, the phenolic hydroxyl group is alternately alkylated with an alkylating agent such as methyl iodide. The calixarene compound obtained by alternately alkylating the obtained phenolic hydroxyl group can be produced by reacting with a phosphorus compound having an alkylene group having a leaving group at the end of the alkylene group (C. Wieser, D Matt, et al 1997 J. Chem. Soc., Dalton Trans, 2391).
Taking p-tert-Bu-phenol as an example of the substituted phenol, a specific production example is shown below.

Shown in Para-tert-butyl-calix [6] arene was refluxed with methyl iodide in acetone in the presence of potassium carbonate for 39 hours in para-tert in which phenolic hydroxyl groups were alternately methylated in 25% yield. -Butyl-calix [6] arene was obtained. This was reacted with tosyloxymethyldiphenylphosphine oxide in toluene at 90 ° C. for 2 hours in the presence of sodium hydride to obtain the corresponding phosphine oxide derivative in 59% yield. The FD-MS m / z of the obtained compound was 1657 [M ⁺ ], which was consistent with the calculated value. The δ value of ³¹ P-NMR (CDCl 3) was 26.7. This was reduced with trihydrophenylsilane in toluene to obtain the desired calix [6] arene compound (1). The m / z of FD-MS of this compound was 1609 [M ⁺ ], which was consistent with the calculated value. The δ value of ³¹ P-NMR (CDCl ₃ ) was −17.1. Elemental analysis agreed with the calculated values. The calix [6] arene compound (1) obtained in the above example has a cone conformation in the solid state from the result of structural analysis, and this conformation is measured by proton, carbon NMR and ROESY measurement. From the results, it was maintained even in a solution state in a temperature range of −55 ° C. to 80 ° C.

The transition metal complex of the calixarene compound represented by the general formula (II) of the present invention is produced by reacting the above-described compound represented by the general formula (I) of the present invention with a transition metal compound in a solvent. be able to. Examples of transition metal compounds include halides such as chlorides of transition metals, various salts such as sulfates and nitrates, complexes such as 1,5-cyclooctadiene (cod) complexes, and complex salts thereof. Specifically, for example, tetrafluoroborate, tetraphenylborate, [Rh (COD) ₂ ] BF ₄ , [Ir (COD) ₂ ] BF ₄ , [Rh (COD) (THF) ₂ ] of (cod) complex BF ₄ , [Ir (COD) (THF) ₂ ] BF _{4 and the} like can be mentioned. Moreover, olefins, such as ethylene, can also be used instead of 1,5-cyclooctadiene.
Examples of the solvent include halogenated hydrocarbons such as dichloromethane and dichloroethane, aromatic hydrocarbons such as toluene, acetone, ether, THF, acetonitrile and the like.
This reaction can usually be carried out at room temperature, but it can also be carried out by heating or cooling if necessary.
For the calix [6] arene compound exemplified above, an example of the production of the metal complex represented by the general formula (II) of the present invention is shown in the following scheme II.

The calix [6] arene compound (1) obtained by the method exemplified above is converted into Ir (cod) (THF) ₂ (BF ₄ ), Ir (cod) (THF) ₂ (BPh ₄ ), or Rh (cod). (THF) ₂ (BF ₄ ) and dichloromethane were reacted at room temperature for 1 to 3 hours, respectively, to obtain metal complexes (3a to 3c) of the target calix [6] arene compound. These compounds were confirmed by ¹ H-NMR, ¹³ C-NMR, ³¹ P-NMR, ESI-MS, and elemental analysis.

The result of the X-ray structural analysis of the metal complex (3a) of the calix [6] arene compound of the iridium complex (X = BF ₄ ) obtained in the above example is shown in FIG. In FIG. 1, the indication of the phenyl ring bonded to the phosphorus atom is omitted. As a result, as shown in FIG. 1, it was clarified that it has a capsule structure composed of two molecules of calixarene and three molecules of metal. This complex had nano-sized vacancies in the molecule, and the distance between Ir-Ir metals was 14.6 to 14.9 mm. The calix [6] arene moiety in the complex has a cone conformation, and the angle between the plane composed of iridium metal of 3 atoms and the plane composed of six methylene carbons of the calixarene is 7. It had a structure tilted 6 °.
The capsule-type iridium and rhodium complexes (3a to 3c) were found to exhibit fractional behavior from the results of temperature-variable phosphorus NMR measurement. For example, in an iridium complex, a spectrum showing one broad peak is obtained in phosphorus NMR measurement at room temperature in methylene chloride, whereas three non-equivalent phosphorus atoms are obtained in the measurement at −60 ° C. As a result, a peak corresponding to was obtained. It was confirmed by NMR measurement that the rhodium complex also showed the same behavior.
Furthermore, with regard to the fractional behavior in the solution state, an interesting result was obtained in that it showed completely different properties depending on the molecular size of the solvent used. Specifically, when phosphorous NMR measurement was performed at room temperature using chloroform, methylene chloride, naphthalene, and cumene as a solvent for a capsule type iridium complex, only one broad peak was shown, In the measurement using 2,2,2-tetrachloroethane, benzene, toluene, o-xylene, m-xylene or the like as a solvent, spectra showing peaks corresponding to three types of non-equivalent phosphorus atoms were obtained.

For example, phosphorus NMR spectrum of capsule-type iridium complex in methylene dichloride and deuterated 1,1,2,2-tetrachloroethane of metal complex (3a) of calix [6] arene compound of iridium complex (X = BF ₄ ) Is shown in FIG. The upper part of the figure shows the case of methylene dichloride at room temperature, and the lower part shows the case of heavy 1,1,2,2-tetrachloroethane at room temperature. As a result, it is considered that solvent molecules such as 1,1,2,2-tetrachloroethane take in the pores of the capsule-type metal complex as guest molecules to control the dynamic behavior of the complex molecules.
These results indicate that the vacancies of the capsule-type iridium and rhodium complexes of the present invention function as a nanoscale molecular control field capable of molecular recognition in a size-selective manner.

Furthermore, as a result of experiments on various molecules, in the example of the metal complex of the calix [6] arene compound of the present invention, a molecular species in the range of about 0.81 to 1.03 nm was used as a guest without depending on the metal species. It was found that it can be taken up or included. This result is schematically shown in FIG. The upper part of FIG. 3 shows the size of molecular species and the molecular species that can be incorporated, and the lower part schematically shows the measurement results of ³¹ P-NMR.
From these results, it was found that the metal complex of the calixarene compound of the present invention has a nano-controlled space according to the size of the calixarene, and incorporates molecules of a specific size into this space. .
Such an action of the metal complex of the present invention is useful as an adsorbing material, and it can take in molecular species of a specific size by molecular sieving action, particularly nano-order molecular sieving action, and fractionate them. Further, it is presumed that the nano-controlled space can be used as a catalyst having high substrate selectivity in olefin hydrogenation, hydroformylation, hydrosilylation, and cross-coupling reactions.

The present invention provides a novel calixarene compound and a metal complex thereof, and the metal complex of the present invention has a nano-controlled space according to the size of the calixarene compound, and has a molecule of a specific size. Species can be selectively incorporated into the space as a guest compound, which is useful not only as a selective molecular adsorption material, but also due to the presence of complexed metal atoms in the space. It can also be used as a chemical reaction field, and is also useful as a material for providing a chemical reaction field having a high degree of substrate selectivity controlled in nano order.
That is, the cyclic metal compound in the present invention has a size selective molecular recognition ability with respect to an organic compound, and can be expected to be used as a catalyst having a novel nano-controlled space field.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.

Production Example of Calixarene Compound 5,11,17,23,29,35-Hexa (t-butyl) -37,39,41-tris (diphenylphosphinoylmethoxy) -38,40,42-trimethoxycalix [ 6] Preparation of arene (1) In a 1 L three-necked flask, 5,11,17,23,29,35-hexa (t-butyl) -37,39,41-trimethoxy-38,40,42-trihydroxy Calix [6] arene (5.08 g, 5.0 mmol) and NaH (3.60 g, 0.15 mol) were suspended in 120 mL toluene. Tosyloxymethyldiphenylphosphine oxide (6.57 g, 17.0 mmol) was added to the mixture and stirred at 90 ° C. for 2 days. The reaction mixture was cooled to room temperature, and excess NaH was slowly neutralized with 3% HCl, followed by ether extraction. After the solvent was distilled off, phosphine oxide was obtained by recrystallization using ethyl acetate / n-hexane (yield 4.9 g, 59%).
The obtained phosphine oxide (1.0 g, 0.603 mmol) was dissolved in 15 mL of toluene, and phenylsilane (1.96 g, 18.1 mmol) was added. The reaction mixture was stirred for 2 days under toluene reflux, and the solvent was distilled off. By performing column chromatography using ethyl acetate / n-hexane (1:25), 0.78 g of an intended product was obtained in an 80% yield.

Mp 254-255 ° C.
Mass spectrometry (FD-MS): m / z 1609 ([M ⁺ ]).
¹ H-NMR (CDCl ₃ ): δ
0.75 (s, 27H), 1.34 (s, 27H),
2.12 (s, 9H, OCH ₃ ),
3.30 (d, 6H, J = 15 Hz, ArCH ₂ Ar),
4.42 (d, 6H, J = 15 Hz, ArCH ₂ Ar),
4.72 (d, 6H, ² J _HP = 4 Hz, OCH ₂ PPh ₂ ),
6.59 (s, 6H), 7.19 (s, 6H),
7.31-7.37 (m, 18H), 7.60-7.64 (m, 12H).
¹³ C-NMR (CDCl ₃ ): δ
30.22 (ArCH ₂ Ar), 31.31, 31.70, 34.23,
34.44, 60.24 (OCH ₃ ),
74.44 (d, ¹ J _CP = 11 Hz, OCH ₂ PPh ₂ ), 124.0,
128.3, 128.9 (d, ³ J _CP = 7 Hz), 129.3, 133.3
133.5 (d, ² J _CP = 18.5 Hz), 133.8,
136.7 (d, ¹ J _CP = 12 Hz), 146.0, 146.3,
153.1 (d, ³ J _CP = 6 Hz), 154.8.
³¹ P-NMR (CDCl ₃ ): δ
-17.1.
Elemental analysis as C ₁₀₈ H ₁₂₃ O ₆ P ₃ :
Calculated C, 80.57; H, 7.70.
Found C, 80.64; H, 7.71.

Example of production of calixarene compound metal complex (capsule complex) (3) Iridium complex (3a)
[Ir (COD) ₂ ] (BF ₄ ) (0.024 mmol) was suspended in 2 mL of dichloromethane in a 50 mL eggplant flask under an argon gas atmosphere, and the calixarene phosphorus compound (1) (0. 031 mmol) dissolved in dichloromethane (6 mL) was added to the flask. The reaction mixture was stirred at room temperature for 3 hours, the solvent was distilled off, and recrystallization from methylene chloride / ether gave the desired product in 92% yield.
¹ H-NMR (CD ₂ Cl ₂ ): 20 ° C., δ
0.68 (s, 54H), 1.27 (s, 54H),
1.87 (brs, 18H, OCH ₃ ),
2.11 [br, 12H, methylene-H (cod)],
2.29 [br, 12H, methylene-H (cod)],
3.49 (brd, 24H, ArCH ₂ Ar),
4.30 (s, 12H, OCH ₂ PPh ₂ ),
5.05 [(br, 12H, olefin-H (cod)),
6.35 (s, 12H), 6.70-8.80 (m, 72H).
³¹ P-NMR (CD ₂ Cl ₂ ): 20 ° C., δ
16.3;
³¹ P-NMR (CD ₂ Cl ₂ ): −60 ° C., δ
15.6 (d, ² J _PP = 17 Hz), 17.3 (s),
18.5 (d, ² J _PP = 17 Hz).
As elemental analysis _{C 240 H 282 O 12 P 6} Ir 3 B 3 F 12 · 3CH 2 Cl 2;
Calculated value; C, 62.95; H, 6.26.
Found: C, 62.45; H, 6.37.

Production of Rhodium Complex (3c) [Rh (COD) ₂ ] (BF ₄ ) (0.024 mmol) was suspended in 2 mL of dichloromethane in a 50 mL eggplant flask under an argon gas atmosphere, and the calixarene phosphorus produced in Example 1 was suspended. What melt | dissolved the compound (1) (0.031 mmol) in the dichloromethane (6 mL) was added in the flask. The reaction mixture was stirred at room temperature for 3 hours, the solvent was distilled off, and recrystallization from methylene chloride / ether gave the desired product in 84% yield.
ESI-MS: m / z 1970 ([10-2 (BF ₄ ⁻ )] ²⁺ ),
^{_{1284 ([10-3 (BF 4 -}} )] 3+).
¹ H-NMR (CD ₂ Cl ₂ , 20 ° C.); δ
0.68 (s, 54H), 1.35 (s, 54H),
2.02 (brs, 18H, OCH ₃ ),
2.32 [br, 12H, methylene-H (cod)],
2.46 [br, 12H, methylene-H (cod)],
3.50 (brd, 24H, ArCH ₂ Ar),
4.68 (br, 12H, OCH ₂ PPh ₂ ),
5.06 [(br, 12H, olefin-H (cod)),
6.34 (s, 12H), 6.70-8.80 (m, 72H);
In the measurement at −60 ° C., the proton of the tert-butyl group was separated into 6 singlets. That is, δ
0.40 (s, 9H), 0.53 (s, 9H), 0.67 (s, 9H),
1.09 (s, 9H), 1.30 (s, 9H), 1.63 (s, 9H);
¹³ C-NMR (CD ₂ Cl ₂ , 20 ° C.): δ
30.32, 30.93, 33.30, 33.70;
³¹ P-NMR (CD ₂ Cl ₂ ): 20 ° C., δ
26.0 (d, ¹ J _RhP = 140 Hz);
³¹ P-NMR (CD ₂ Cl ₂ ): −60 ° C., δ
24.7 (dd, ¹ J _RhP = 134 Hz, ² J _PP = 33 Hz),
27.3 (d, ¹ J _RhP = 135 Hz),
27.7 (dd, ¹ J _RhP = 135 Hz, ² J _PP = 33 Hz);
As elemental analysis _{C 240 H 282 O 12 P 6} Rh 3 B 3 F 12 · CH 2 Cl 2;
Calculated value; C, 68.94; H, 6.82.
Found: C, 69.21; H, 6.71.

Production of calixarene metal complex (capsule complex) and tetrachloroethane inclusion complex (2 · Cl ₂ CHCHCl ₂ ) (iridium complex (3a · Cl ₂ CHCHCl ₂ ))
In a 20 mL eggplant flask, the iridium complex (3a) (5 mg) prepared in Example 2 was dissolved in tetrachloroethane (0.5 mL) and stirred at room temperature for 3 hours. By distilling off the solvent, a tetrachloroethane inclusion iridium complex (3a · Cl ₂ CHCHCl ₂ ) was quantitatively obtained.
¹ H-NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
0.51 (s, 18H), 0.64 (s, 18H), 0.70 (s, 18H),
1.16 (s, 18H), 1.21 (s, 6H),
2.95 (d, 2H, J = 15 Hz), 3.35 (d, 2H, J = 15 Hz),
3.42-3.60 (m, 6H), 3.67 (d, 2H, J = 15 Hz),
4.12 (brs, 6H), 4.27 (brs, 6H),
4.52-4.73 (m, 6H), 4.84-4.96 (m, 2H),
5.00-5.10 (m, 2H), 5.12-5.22 (m, 2H),
6.07 (s, 2H), 6.14 (s, 2H), 6.23 (s, 2H),
6.34 (s, 2H), 6.43 (s, 2H), 6.46-6.54 (m, 8H), 6.56-6.70 (m, 4H), 6.73 (s, 2H),
6.90-7.28 (m, 24H), 7.32-7.70 (m, 26H),
7.80-7.90 (m, 2H), 7.92-8.02 (m, 2H),
8.10-8.32 (m, 4H), 8.40-8.52 (m, 2H),
8.72-8.92 (m, 6H);
¹³ C-NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
30.83, 30.92, 31.01, 31.55, 31.82, 32.05
33.84, 33.87, 33.89, 34.10, 34.38, 34.81;
³¹ P-NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
15.3 (d, ² J _PP = 18 Hz), 15.9 (d, ² J _PP = 18 Hz),
16.4 (s).

Rhodium complex (3c · Cl ₂ CHCHCl ₂ )
In a 20 mL eggplant flask, the rhodium complex (3c) (5 mg) prepared in Example 3 was dissolved in (0.5 mL) in tetrachloroethane and stirred at room temperature for 3 hours. By distilling off the solvent, a tetrachloroethane inclusion rhodium complex (3c · Cl ₂ CHCHCl ₂ ) was obtained quantitatively.
¹ H-NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
0.51 (s, 18H), 0.64 (s, 18H), 0.70 (s, 18H),
1.15 (s, 18H), 1.22 (s, 6H), 1.34 (s, 18H),
1.69 (s, 18H), 1.88-2.30 (m, 24H),
2.38-2.60 (m, 12H), 2.64-2.83 (m, 6H),
3.00 (d, 2H, J = 15 Hz), 3.36 (d, 2H, J = 15 Hz),
3.42-3.60 (m, 6H), 3.70 (d, 2H, J = 15 Hz),
4.50 (brs, 6H), 4.56-4.82 (m, 12H),
4.87-4.98 (m, 2H), 5.02-5.12 (m, 2H),
5.14-5.24 (m, 2H), 6.06 (s, 2H), 6.14 (s, 2H), 6.23 (s, 2H), 6.33 (s, 2H), 6 .42 (s, 2H),
6.44-6.56 (m, 8H), 6.58-6.68 (m, 4H),
6.73 (s, 2H), 6.88-6.94 (m, 2H),
6.95-7.02 (m, 2H), 7.04-7.23 (m, 20H),
7.32-7.66 (m, 26H), 7.82-7.92 (m, 2H),
7.94-8.06 (m, 2H), 8.23-8.44 (m, 4H),
8.58-8.88 (m, 8H).
¹³ C-NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
30.83, 30.93, 31.01, 31.55, 31.82, 32.06
33.83, 33.86, 33.88, 34.09, 34.37, 34.81;
³¹ P NMR (Cl ₂ CDCDCl ₂ , 20 ° C.): δ
24.8 (dd, ¹ J _RhP = 135 Hz, ² J _PP = 32 Hz),
25.0 (dd, ¹ J _RhP = 135 Hz, ² J _PP = 32 Hz),
26.6 (d, ¹ J _RhP = 136 Hz).

  The present invention provides a novel metal complex of a calixarene compound having a nano-controlled space with high substrate selectivity, and the metal complex of the present invention is industrially useful as an adsorbing material having a molecular sieving action. In addition, it provides a nanospace as a chemical reaction field with high substrate selectivity, and is extremely useful in the synthetic chemical industry. Moreover, the calixarene compound of the present invention is industrially useful as an intermediate in producing the above-described metal complex of the present invention.

FIG. 1 shows the results of X-ray structural analysis of the metal complex (3a) of the calix [6] arene compound of the present invention. In FIG. 1, the indication of the phenyl ring bonded to the phosphorus atom is omitted. FIG. 2 shows the calix [6] arene compound metal complex (3a) of the present invention in methylene dichloride at room temperature (upper part of FIG. 2) and in heavy 1,1,2,2-tetrachloroethane (of FIG. 2). The ³¹ P-NMR spectrum of the capsule type iridium complex in the lower part) is shown. FIG. 3 schematically shows the results of guest molecule incorporation or inclusion by the metal complex of the present invention, taking the calix [6] arene compound metal complex of the present invention as an example. The upper part of FIG. 3 shows the size of molecular species and the molecular species that can be incorporated, and the lower part schematically shows the measurement results of ³¹ P-NMR.

Claims (14)

Formula (I)

Wherein R ¹ represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, and R ² and R ³ each independently represents a hydrogen atom, a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, X is C represents an alkylene group of _{1 to 10} , Y represents an aryl group or an aryloxy group, and n represents an integer of 3 to 6.)
A calixarene compound in which phosphorous atoms are introduced alternately. The calixarene compound according to claim 1, wherein R ² and R ³ are each a substituent bonded to the para position of the oxygen atom.   The calixarene compound according to claim 1 or 2, wherein the calixarene compound is a calix [6] arene compound wherein n is 3.   The calixarene compound according to any one of claims 1 to 3, wherein Y is an aryl group.   A transition metal complex of calixarene obtained by reacting the calixarene compound according to any one of claims 1 to 4 with a transition metal compound. The transition metal complex of calixarene is the general formula (II)

(Wherein R ¹ represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, R ² and R ³ each independently represents a hydrogen atom, a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group, and X is C represents an alkylene group of _{1 to 10} , Y represents an aryl group or an aryloxy group, M represents a transition metal atom, Z represents an anionic group, m represents a value corresponding to the valence of the transition metal M And n represents an integer of 3 to 6.)
A transition metal complex of calixarene represented by   The transition metal complex of calixarene according to claim 5 or 6, wherein the transition metal is rhodium or iridium. The transition metal complex of calixarene compound according to any one of claims 5 to 7, wherein R ² and R ³ are each a substituent bonded to the para position of the oxygen atom.   The transition metal complex of a calixarene compound according to any one of claims 5 to 8, wherein the calixarene compound is a calix [6] arene compound wherein n is 3.   Y is an aryl group, The transition metal complex of the calixarene compound in any one of Claims 5-9.   A method for producing a transition metal complex of a corresponding calixarene compound by reacting the calixarene compound according to any one of claims 1 to 4 with a transition metal compound in a solvent.   The production method according to claim 11, wherein the solvent is dichloroethane.   The adsorption material which consists of a transition metal complex of the calixarene compound in any one of Claims 5-10. The adsorbent material according to claim 13, wherein the adsorbent material has a nano-order molecular sieving action.

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