JP2020069472A - Solid catalyst and method for producing carbonyl compound and hydrogen using the same - Google Patents

Abstract

To provide an active solid catalyst which is excellent in the dehydrogenation reaction of alcohols.SOLUTION: There is provided a solid catalyst which is composed a transition metal-containing meso-porous organic silica represented by the following formula (1): [in the formula (1), M is iridium or the like, Lis a cyclopentadienyl group or the like, Lis an aquo ligand, a hydroxyl group or the like, at least one group of Rto Rand at least one group of Rto Ris represented by the following formula (2): -Y-(-Si(R)(OR)-O-)-*(2)(in the formula (2), Y is a divalent or trivalent organic group or the like, Ris an alkyl group having 1 to 8 carbon atoms or the like, Ris a hydrogen atom or the like)] and is used in the dehydrogenation reaction of alcohols or the like.SELECTED DRAWING: None

Description

  The present invention relates to a solid catalyst for dehydrogenation reaction, and a method for producing a carbonyl compound and hydrogen using the same, and more specifically, a solid catalyst used for dehydrogenation reaction of alcohols, formic acid and formate salts, and the use thereof. And a method for producing hydrogen.

  It is known that mesoporous organic silica having a bipyridine group coordinated to a transition metal atom of Group 9 of the periodic table such as iridium exhibits excellent catalytic activity in the boration reaction of an aromatic compound (JP-A-2014-2014). 193457 gazette (patent document 1)). However, since this mesoporous organic silica does not show catalytic activity in the dehydrogenation reaction of alcohols, formic acid and formate salts, carbonyl compounds can be produced from alcohols and hydrogen can be produced from alcohols, formic acid and formate salts. It could not be used as a solid catalyst when it was manufactured.

  On the other hand, a metal complex in which bipyridone is coordinated with a transition metal atom such as iridium is known to exhibit excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formate salts, and a carbonyl compound is converted from an alcohol. It is used as a homogeneous catalyst for the production or production of hydrogen from alcohols, formic acid or formate (International Publication No. 2013/125020 (Patent Document 2)). However, a metal complex in which dihydroxybipyridine, a tautomer of bipyridone, is coordinated to a transition metal atom such as iridium does not show high catalytic activity in the dehydrogenation reaction of alcohols, formic acid, and formate salts. A catalyst amount of several mol% or more is required in the case of producing a carbonyl compound from bisphenol, or in producing hydrogen from an alcohol, formic acid or formate salt.

  When a metal complex in which bipyridone is coordinated to the transition metal atom is used as a homogeneous catalyst for dehydrogenation of an aqueous methanol solution, carbon dioxide as a by-product shifts the reaction solution to an acidic side and Since the production reaction is stopped, in order to continuously produce hydrogen by using the dehydrogenation reaction, it was necessary to add a base to maintain the reaction solution in a neutral to basic state.

JP, 2014-193457, A International Publication No. 2013/125020

  The present invention has been made in view of the above problems of the prior art, a solid catalyst having excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formate salts, and carbonyl compounds using this solid catalyst. And a method for producing hydrogen.

  As a result of intensive studies to achieve the above object, the present inventors mixed mesoporous organic silica having a hydroxyl group-containing bipyridine group with a compound containing a transition metal atom selected from iridium, rhodium, and ruthenium. By forming a metal complex in which the hydroxyl group-containing bipyridine group is coordinated to the transition metal atom, the compound containing the transition metal atom is immobilized on the outer surface or the inner surface of the pores of the mesoporous organic silica. Furthermore, they have found that the obtained transition metal-containing mesoporous organic silica exhibits excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formate salts, and have completed the present invention.

  That is, the solid catalyst of the present invention has the following formula (1):

[In the formula (1), M represents a transition metal atom selected from the group consisting of iridium, rhodium and ruthenium, and L ¹ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclopentadienyl group. represents, L ² is the sulfoxide ligand, a nitrogen-containing aromatic ring ligand, amine ligand, a phosphine ligand, the ligand or a hydroxyl group is selected from the group consisting of ether ligands and aquo ligands Represents at least one group out of R ^{1 to} R ⁴ and at least one group out of R ^{5 to} R ⁸ is a hydroxyl group, and at least one group out of the remaining groups in R ^{1 to} R ⁴ and R ^At least one group of the remaining groups of ^{5 to} R ⁸ is represented by the following formula (2):

(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group and an imide group. An organic group or a single bond, R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, R ^b represents a hydrogen atom or a silyl group, k is 1 or 2, and i Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a combination of i and j is plural in each group represented by the formula (2). Independent, * is the binding site with the adjacent structure)
Which is a group represented by the following formula, wherein the remaining group of R ^{1 to} R ^{4 and} the remaining group of R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, It is a monovalent or divalent organic group selected from the group consisting of an alkoxy group, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group and a cyano group, and R ⁴ and R ⁸ are They may combine with each other to form -CH = CH-]
A structure represented by, a transition metal-containing mesoporous organic silica having a coordination structure selected from the group consisting of its stereoisomers and tautomers,
It is characterized by being used for a dehydrogenation reaction of at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate salts.

In such a solid catalyst, the structure represented by the formula (1) is arranged on the outer surface if it is arranged on the inner surface (pore wall) of the pores of the transition metal-containing mesoporous organic silica. The transition metal-containing mesoporous organic silica may be contained in the skeleton of the transition metal-containing mesoporous organic silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “first transition metal-containing mesoporous organic silica”). May be bonded to the inner surface (pore wall) of the mesoporous silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “second transition metal-containing mesoporous organic silica”). Furthermore, in the solid catalyst of the present invention, M in the formula (1) is iridium, L ¹ is a substituted or unsubstituted cyclopentadienyl group, and L ² is an aco ligand or a hydroxyl group. Preferably, R ¹ and R ⁵ are hydroxyl groups, and R ² and R ⁶ are also groups represented by the above formula (2).

  The method for producing a carbonyl compound of the present invention is a method characterized in that an alcohol is dehydrogenated using the solid catalyst of the present invention to produce a carbonyl compound. Furthermore, the method for producing hydrogen according to the present invention comprises dehydrogenating at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate salts using the solid catalyst of the present invention to generate hydrogen. The method is characterized by: Further, in such a method for producing hydrogen of the present invention, it is possible to carry out dehydrogenation of the oxygen-containing compound in a gas phase.

  The reason why the solid catalyst of the present invention exhibits excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formic acid salts is not always clear, but the present inventors speculate as follows. That is, in the solid catalyst of the present invention, since the hydroxyl group-containing bipyridine group constituting the pore wall of the mesoporous organic silica is coordinated to the transition metal atom such as iridium, the hydroxyl group-containing bipyridine is coordinated to the transition metal atom. A local structure (catalyst site) similar to that of the homogeneous metal complex is formed in an isolated state inside and outside the pore walls of mesoporous organic silica. Since this catalyst site is firmly fixed inside and outside the pore walls, it is presumed that unnecessary interaction of the catalyst sites does not occur during the dehydrogenation reaction and high catalytic activity is exhibited. Further, in the vicinity of the catalyst site fixed on the inside and outside of the pore wall, since there is a functional group such as silanol group, not only when the bipyridone group is coordinated to the transition metal atom, hydroxyl group It is presumed that high catalytic activity is exhibited even when the contained bipyridine group is coordinated.

  On the other hand, it is presumed that the homogeneous metal complex in which the hydroxyl group-containing bipyridine is coordinated with the transition metal atom is aggregated during the dehydrogenation reaction, so that the catalyst is deactivated and the reaction yield is reduced.

  According to the present invention, it is possible to obtain a solid catalyst having excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formic acid salts. Moreover, by using this solid catalyst, it becomes possible to produce a carbonyl compound and hydrogen in a high yield. Furthermore, by using this solid catalyst, it becomes possible to carry out the dehydrogenation reaction in the gas phase, and when continuously producing hydrogen, carbon dioxide, which is a by-product, can be discharged to the outside of the system. The system does not become acidic and the addition of base is unnecessary.

9 is a graph showing an X-ray diffraction pattern of a mesoporous organic silica having a hydroxyl group-containing bipyridine group obtained in Preparation Example C1. It is a graph which shows the nitrogen adsorption / desorption isotherm of the mesoporous organic silica which has the hydroxyl group-containing bipyridine group obtained in Preparation Example C1. 9 is a graph showing an X-ray diffraction pattern of mesoporous silica having a hydroxyl group-containing bipyridine group obtained in Preparation Example C2. It is a graph which shows the nitrogen adsorption / desorption isotherm of the mesoporous silica which has the hydroxyl group-containing bipyridine group obtained in Preparation Example C2. It is a graph which shows the X-ray-diffraction pattern of the mesoporous silica which has a hydroxyl group-containing bipyridine group obtained in Preparation Example C3. It is a graph which shows the nitrogen adsorption / desorption isotherm of the mesoporous silica which has the hydroxyl group-containing bipyridine group obtained in Preparation Example C3. 9 is a graph showing an X-ray diffraction pattern of a mesoporous organic silica having a hydroxyl group-containing bipyridine group obtained in Preparation Example C4. It is a graph which shows the nitrogen adsorption / desorption isotherm of the mesoporous organic silica which has the hydroxyl group-containing bipyridine group obtained in Preparation Example C4. 3 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1. 3 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous organic silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1. 3 is a graph showing an X-ray diffraction pattern of a mesoporous organic silica having a bipyridone group coordinated to Ir obtained in Synthesis Example 2. 3 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous organic silica having a bipyridone group coordinated to Ir obtained in Synthesis Example 2. 9 is a graph showing an X-ray diffraction pattern of mesoporous silica having a bipyridine group having a hydroxyl group coordinated to Ir obtained in Synthesis Example 3. 7 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 3. 9 is a graph showing an X-ray diffraction pattern of mesoporous silica having a bipyridone group coordinated to Ir, which is obtained in Synthesis Example 4. 9 is a graph showing a nitrogen adsorption / desorption isotherm of mesoporous silica having a bipyridone group coordinated to Ir obtained in Synthesis Example 4. 9 is a graph showing an X-ray diffraction pattern of mesoporous silica having a bipyridine group having a hydroxyl group coordinated to Ir, which is obtained in Synthesis Example 5. 9 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 5. 9 is a graph showing an X-ray diffraction pattern of a mesoporous organic silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 6. 7 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous organic silica having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 6. 9 is a graph showing an X-ray diffraction pattern of the mesoporous organic silica having a bipyridone group coordinated to Ir obtained in Synthesis Example 7. 7 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous organic silica having a bipyridone group coordinated to Ir obtained in Synthesis Example 7. 3 is a graph showing an X-ray diffraction pattern of the mesoporous organic silica having a bipyridine group coordinated to Ir obtained in Comparative Synthesis Example 1. 3 is a graph showing a nitrogen adsorption / desorption isotherm of the mesoporous organic silica having a bipyridine group coordinated to Ir obtained in Comparative Synthesis Example 1. It is a graph which shows the reaction yield of the acetophenone in the dehydrogenation liquid phase reaction of 1-phenyl ethanol implemented in Examples 1-2 and the comparative example 1. It is a graph which shows the reaction yield of the acetophenone in the dehydrogenation liquid phase reaction of 1-phenyl ethanol implemented in Examples 3-4 and Comparative Example 1. Reaction yield of hydrogen in dehydrogenation liquid phase reaction of aqueous methanol solution carried out in Example 5 and Comparative Example 2, dehydrogenation reaction of aqueous formic acid solution carried out in Example 6 and dehydrogenation reaction of aqueous sodium formate solution carried out in Example 7. It is a graph which shows a rate. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Example 8. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Example 9. 7 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Comparative Example 3. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Example 10. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Example 11. Dehydrogenated liquid phase reaction of 1- (4-methoxyphenyl) ethanol carried out in Example 12, Dehydrogenated liquid phase reaction of 1- (2-methoxyphenyl) ethanol carried out in Example 13, carried out in Example 14. 1 is a graph showing reaction yields of various ketones in a dehydrogenation liquid phase reaction of 1- (4-tert-butylphenyl) ethanol and a dehydrogenation liquid phase reaction of 1- (4-chlorophenyl) ethanol carried out in Example 15. From the left, the bar of each Example shows the reaction yield in the new use, the first reuse, and the second reuse. Dehydrogenation liquid phase reaction of 1- (4-bromophenyl) ethanol carried out in Example 16, Dehydrogenation liquid phase reaction of 1- [4- (trifluoromethyl) phenyl] ethanol carried out in Example 17, Example 18 is a graph showing the reaction yields of various ketones in the dehydrogenation liquid phase reaction of 1- (4-cyanophenyl) ethanol carried out in 18 and the dehydrogenation liquid phase reaction of 1-phenyl-1-propanol carried out in Example 19. Yes, the bar in each example shows the reaction yields from new use, first reuse, and second reuse from the left. 2-Octanol dehydrogenation liquid phase reaction carried out in Example 20, 6-undecanol dehydrogenation liquid phase reaction carried out in Example 21, cyclohexanol dehydrogenation liquid phase reaction carried out in Example 22, Example 23 FIG. 4 is a graph showing the reaction yields of various ketones in the dehydrogenation liquid phase reaction of cyclopentanol carried out in Example 1. The bars in each Example are from the left in the new use, the first reuse, and the second reuse. The reaction yield is shown. Dehydrogenation liquid phase reaction of benzyl alcohol carried out in Example 24, Dehydrogenation liquid phase reaction of 4-methoxybenzyl alcohol carried out in Example 25, Dehydrogenation liquid phase reaction of 4-bromobenzyl alcohol carried out in Example 26 FIG. 28 is a graph showing the reaction yields of various aldehydes in the dehydrogenation liquid phase reaction of cyclohexanemethanol carried out in Example 27, and the bar of Example 24 shows, from the left, new use, first reuse, and second use. The reaction yield in reuse is shown, and the bars in Examples 25 to 27 show the reaction yield in new use. Carbonyl in the dehydrogenation reaction of 2-octanol (new use), the dehydrogenation reaction of benzyl alcohol (first reuse), and the dehydrogenation reaction of 1-phenylethanol (second reuse) performed in Example 28. It is a graph which shows the reaction yield of a compound. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an aqueous methanol solution carried out in Example 29. 20 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of an ethanol aqueous solution carried out in Example 30. 9 is a graph showing a hydrogen generation rate in a dehydrogenation gas phase reaction of 2-propanol carried out in Example 31.

  Hereinafter, the present invention will be described in detail with reference to its preferred embodiments.

<Solid catalyst>
First, the solid catalyst of the present invention will be described. The solid catalyst of the present invention has the following formula (1):

[In the formula (1), M represents a transition metal atom selected from the group consisting of iridium, rhodium and ruthenium, and L ¹ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclopentadienyl group. represents, L ² is the sulfoxide ligand, a nitrogen-containing aromatic ring ligand, amine ligand, a phosphine ligand, the ligand or a hydroxyl group is selected from the group consisting of ether ligands and aquo ligands Represents at least one group out of R ^{1 to} R ⁴ and at least one group out of R ^{5 to} R ⁸ is a hydroxyl group, and at least one group out of the remaining groups in R ^{1 to} R ⁴ and R ^At least one group of the remaining groups of ^{5 to} R ⁸ is represented by the following formula (2):

(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group and an imide group. An organic group or a single bond, R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, R ^b represents a hydrogen atom or a silyl group, k is 1 or 2, and i Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a combination of i and j is plural in each group represented by the formula (2). Independent, * is the binding site with the adjacent structure)
Which is a group represented by the following formula, wherein the remaining group of R ^{1 to} R ^{4 and} the remaining group of R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, It is a monovalent or divalent organic group selected from the group consisting of an alkoxy group, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group and a cyano group, and R ⁴ and R ⁸ are They may combine with each other to form -CH = CH-]
And a transition metal-containing mesoporous organic silica having a coordination structure selected from the group consisting of a structure represented by the formula, its stereoisomers and tautomers. In the present invention, such a solid catalyst is used for the dehydrogenation reaction of at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate salts, and exhibits excellent catalytic activity.

  In the solid catalyst of the present invention, the structure represented by the formula (1) is arranged on the outer surface if it is arranged on the inner surface (pore wall) of the pores of the transition metal-containing mesoporous organic silica. The transition metal-containing mesoporous organic silica may be contained in the skeleton of the transition metal-containing mesoporous organic silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “first transition metal-containing mesoporous organic silica”). May be bonded to the inner surface (pore wall) of the mesoporous silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “second transition metal-containing mesoporous organic silica”).

  The solid catalyst of the present invention contains a bipyridine group having a hydroxyl group, as shown by the formula (1), and a transition metal complex is formed by coordinating the hydroxyl group-containing bipyridine group with the transition metal atom. Then, this transition metal complex becomes an active site and exhibits a catalytic action. In the solid catalyst of the present invention, it is not necessary that all the hydroxyl group-containing bipyridine groups be coordinated with the transition metal atom. In the first transition metal-containing mesoporous organic silica, the group represented by the formula (2) is a group having a crosslinking point (hereinafter, also referred to as “crosslinking group”), and the siloxane in the crosslinking group is Since the hydroxyl group-containing bipyridine group is three-dimensionally crosslinked by the bond (Si-O bond), the solid catalyst of the present invention exhibits high durability against mechanical action and chemical action.

In the above formula (1), M represents a transition metal atom selected from the group consisting of iridium, rhodium and ruthenium. Among these, iridium is preferable from the viewpoint of high catalytic activity. L ¹ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclopentadienyl group, and the phenyl group and cyclopentadienyl group may have a substituent such as a methyl group. Of these, a substituted or unsubstituted cyclopentadienyl group is preferable from the viewpoint of ease of complex synthesis.

Further, in the above formula (1), L ² is selected from the group consisting of a sulfoxide ligand, a nitrogen-containing aromatic ring ligand, an amine ligand, a phosphine ligand, an ether ligand and an aco ligand. Represents a ligand or a hydroxyl group. Examples of sulfoxide ligands include dimethyl sulfoxide (DMSO), diphenyl sulfoxide, and methylphenyl sulfoxide, and examples of nitrogen-containing aromatic ring ligands include pyridine, picoline, lutidine, 3-chloropyridine, and 4-chloropyridine. Examples of the amine ligand include aniline, toluidine, anisidine, and the like, and examples of the phosphine ligand include triphenylphosphine, trimethylphosphine, tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and tricyclohexylphosphine. Ethoxyphosphine and the like can be mentioned, and as the ether ligand, dimethyl ether, diethyl ether, diisopropyl ether, cyclopentyl methyl ether, methyl-tert-butyl ether, tetrahydrofuran, - methyltetrahydrofuran, anisole. Among these, an aco ligand or a hydroxyl group is preferable from the viewpoint of increasing the catalytic activity and improving the reaction yield.

In the formula (1), at least one group out of R ^{1 to} R ⁴ and at least one group out of R ^{5 to} R ⁸ are hydroxyl groups. When the structure represented by the formula (1) has a hydroxyl group, excellent catalytic activity is exhibited in the dehydrogenation reaction of the oxygen-containing compound. Further, it is preferable that R ¹ and R ⁵ are hydroxyl groups from the viewpoint that the dehydrogenation reaction of the oxygen-containing compound is facilitated by arranging the hydroxyl group near the transition metal atom M.

Further, in the formula (1), at least one group of the remaining groups of R ^{1 to} R ⁴ and at least one group of the remaining groups of R ^{5 to} R ⁸ are the same as those of the formula (2). It is a crosslinking group represented. When the solid catalyst of the present invention is composed of the first transition metal-containing mesoporous organic silica, R ² and R ⁶ are each independently a crosslinking group from the viewpoint that a mesopore structure is easily formed. Preferably. Further, when the solid catalyst of the present invention is composed of the second transition metal-containing mesoporous organic silica, one of R ² and R ⁶ has the above-mentioned crosslinked structure from the viewpoint of its bondability. It is preferably a group.

  Y in the formula (2) is an alkylene group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 1 to 6), an alkenylene group (preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 6). ), An alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an arylene group (preferably having 6 to 12 carbon atoms), an ether group, a carbonyl group, an amino group, an amide group and an imide group. It is a divalent or trivalent organic group or a single bond selected from the group consisting of:

  Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group and the like, examples of the alkenylene group include ethenylene group, propenylene group, butenylene group and the like, and examples of the alkynylene group include ethynylene group, Examples thereof include a propynylene group and a butynylene group. Examples of the arylene group include a monocyclic aromatic ring such as a phenylene group and an aromatic condensed ring such as a naphthylene group and a fluorenylene group.

  Of these divalent or trivalent organic groups and single bonds, an alkylene group and a single bond are preferable from the viewpoint of improving the mechanical strength and chemical stability of the solid catalyst, and an alkylene having 1 to 6 carbon atoms. More preferred are groups and single bonds.

^Ra in the above formula (2) represents an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms or a substituted or unsubstituted allyl group, and the allyl group has a substituent such as a methyl group. May be. Further, R ^b in the formula (2) represents a hydrogen atom or a silyl group, examples of the silyl group include an alkylsilyl group such as a trimethylsilyl group, and R ^b is from the viewpoint of suppressing steric hindrance. A hydrogen atom is preferred.

  Further, * in the formula (2) is a binding site with an adjacent structure. When the solid catalyst of the present invention comprises the first transition metal-containing mesoporous organic silica, the adjacent structure is represented by the formula (1) in the transition metal-containing mesoporous organic silica. A repeating unit having a structure, a structure represented by the formula (3) described later, a structure represented by the formula (4) described below, and the like can be mentioned, and the solid catalyst of the present invention is the second transition metal-containing mesoporous organic silica. When it is composed of, the surface structure of the mesoporous silica is exemplified, and the binding site is preferably bonded to a silicon atom on the surface of the mesoporous silica.

  In the formula (2), k is 1 or 2, i is an integer of 1 to 3 (preferably an integer of 2 to 3), and j is an integer of 0 to 2 (preferably an integer of 0 to 1). And 1 ≦ i + j ≦ 3 (preferably 2 ≦ i + j ≦ 3). In addition, the combination of i and j is independent in each of the plural bridging groups, and does not need to be the same in all the bridging groups in the solid catalyst of the present invention.

In the formula (1), the remaining group of R ^{1 to} R ^{4 and} the remaining group of R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group (preferably having a carbon number). 1 to 12), aryl group (preferably having 6 to 12 carbon atoms), alkoxy group (preferably having 1 to 12 carbon atoms), phenoxy group, acetyl group, benzoyl group, amino group, amide group, imide group, nitro group and It is a monovalent or divalent organic group selected from the group consisting of cyano groups. R ⁴ and R ⁸ may combine with each other to form —CH═CH—.

  Examples of the alkyl group include a methyl group, ethyl group, propyl group and butyl group, and examples of the aryl group include a monocyclic aromatic ring such as a phenyl group, an aromatic condensed ring such as a naphthyl group and a fluorenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

  Among such monovalent or divalent organic groups, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group and a phenoxy group are selected from the viewpoint of improving the mechanical strength and the chemical stability of the solid catalyst. A hydrogen atom is more preferable.

  In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the fixed amount of the transition metal atom per 1 g of the transition metal-containing mesoporous organic silica is 0.01 mmol / g or more. Although not limited, 0.01 to 3.0 mmol / g is preferable, 0.02 to 2.5 mmol / g is more preferable, and 0.05 to 2 from the viewpoint of improving catalytic activity and effectively utilizing transition metal atoms. 0.0 mmol / g is more preferable, 0.075 to 1.5 mmol / g is particularly preferable, and 0.10 to 1.0 mmol / g is most preferable. The amount of such a transition metal atom immobilized can be arbitrarily adjusted according to the content of the hydroxyl group-containing bipyridine group in the mesoporous organic silica having the hydroxyl group-containing bipyridine group, and also the content of the hydroxyl group-containing bipyridine group. The amount can also be adjusted arbitrarily.

  In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the proportion of the structure represented by the formula (1) is not particularly limited as long as it is 1% by mass or more. From the viewpoint of improving the catalytic activity, the first transition metal-containing mesoporous organic silica is preferably 1 to 90% by mass, more preferably 1 to 75% by mass, further preferably 1.5 to 60% by mass, 2.5 to 45% by mass is particularly preferable, 3.0 to 30% by mass is most preferable, and about the second transition metal-containing mesoporous organic silica, 1 to 60% by mass is preferable, and 1.5 to 50% by mass. Are more preferable, 2.0-40 mass% are still more preferable, 2.5-35 mass% are especially preferable.

  When the ratio of the structure represented by the formula (1) is less than 100% by mass, the structure other than the structure represented by the formula (1) (hereinafter, referred to as “other structure”) is represented by the following formula (3). ) And (4):

The structure represented by is preferable, and one of these structures may be contained or both of them may be contained.

In the above formula (3), R ⁹ is a divalent to tetravalent organic group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an arylene group (preferably having 6 carbon atoms). ~ 12) etc. are mentioned. In the formulas (3) and (4), each R ^c independently represents an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms or a substituted or unsubstituted allyl group, and the allyl group is a methyl group or the like. It may have a substituent. In the formulas (3) and (4), R ^d independently represents a hydrogen atom or a silyl group, and the silyl group includes an alkylsilyl group such as a trimethylsilyl group, and R ^d is a steric group. A hydrogen atom is preferable from the viewpoint of being able to suppress obstacles.

  Further, * in the formulas (3) and (4) is a binding site with an adjacent structure. The adjacent structure is represented by the repeating unit having the structure represented by the formula (1) in the transition metal-containing mesoporous organic silica, the structure represented by the formula (3), and the formula (4). And a surface structure of mesoporous silica (preferably a silicon atom on the surface of mesoporous silica).

  In the formulas (3) and (4), r is independently 1 or 2, p is independently an integer of 1 to 3 (preferably an integer of 2 to 3), and q is 0 independently. To 2 (preferably 0 to 1), and 1 ≦ p + q ≦ 3 (preferably 2 ≦ p + q ≦ 3). It should be noted that the combination of p and q is independent in the structure represented by the formula (3) or (4), which exists in plural numbers, and all the combinations of the formula (3) or (4) in the solid catalyst of the present invention. ) Need not be the same in the structure represented by.

  In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the ratio of such other structures is 99 relative to the total amount of the structure represented by the formula (1). There is no particular limitation as long as it is at most% by mass, but from the viewpoint of improving the durability of the catalyst, the first transition metal-containing mesoporous organic silica is preferably 10 to 99% by mass, and 25 to 99% by mass. More preferably, 40 to 98.5 mass% is further preferable, 55 to 97.5 mass% is particularly preferable, 70 to 97.0 mass% is most preferable, and the second transition metal-containing mesoporous organic silica is 40 -99 mass% is preferable, 50-98.5 mass% is more preferable, 60-98.0 mass% is further more preferable, 65-97.5 mass% is especially preferable.

The transition metal-containing mesoporous organic silica according to the present invention has a structure having mesopores (mesopore structure). The pore diameter (central pore diameter) in such a mesopore structure is preferably 1 to 50 nm, more preferably 2 to 30 nm. Further, the total pore volume is preferably 0.1 cm ³ / g or more, more preferably 0.2 cm ³ / g or more. If the central pore diameter and the total pore volume are less than the lower limits, the reaction substrate in the catalytic reaction does not sufficiently diffuse into the mesopores, and the catalytic reaction tends not to proceed sufficiently. Furthermore, in the transition metal-containing mesoporous organic silica, the specific surface area is preferably 100 cm ² / g or more, more preferably 300 cm ² / g or more. If the specific surface area is less than the above lower limit, sufficient catalytic activity tends to not be obtained.

  The central pore diameter can be determined by a DFT (Density-Functional-Theory) method based on the nitrogen adsorption-desorption isotherm, and the total pore volume is t-plot based on the nitrogen adsorption-desorption isotherm. The specific surface area can be determined by the BET (Brunauer-Emmett-Teller) method based on the nitrogen adsorption / desorption isotherm.

  The X-ray diffraction pattern of the transition metal-containing mesoporous organic silica according to the present invention preferably has one or more diffraction peaks at a diffraction angle corresponding to a d value of 1 to 50 nm. The X-ray diffraction peak means that the sample has a periodic structure with a d value corresponding to the peak angle. Therefore, the presence of one or more diffraction peaks at a diffraction angle corresponding to a d value of 1 to 50 nm means that the pores are regularly arranged at intervals of 1 to 50 nm. Means being equipped. In the transition metal-containing mesoporous organic silica having such a regular mesopore structure, the transition metal complex is stably immobilized, and the catalytic activity is excellent.

  Such a solid catalyst of the present invention has, for example, the following formula (1a):

[In the formula ^(1a), R 1 to R ⁸ are the same group as ^R 1 to R ⁸ in the formula (1)]
It can be produced by mixing mesoporous organic silica having a structure represented by and a compound containing a transition metal atom selected from the group consisting of iridium, rhodium and ruthenium. Thereby, the nitrogen atom in the formula (1a) is coordinated with the transition metal atom, and the transition metal-containing mesoporous organic silica represented by the formula (1) is obtained. Such mixing may be carried out in a system different from the catalytic reaction system or in the catalytic reaction system before carrying out the catalytic reaction.

Examples of the compound containing a transition metal atom include the following formula (5):
L ¹ -ML ² (5)
(Formula (5) in, M, ^{L 1} and ^{L 2} are those wherein Formula (1) M, the same as ^{L 1} and ^{L 2)}
The transition metal compound represented by Specific examples of the transition metal _{^{compound, [IrCp * (H 2 O}} ) 3] (OTf) 2, [IrCp * (H 2 O) 3] SO 4, [IrCp * (H 2 O) 3] (PF ₆ ) ₂ , iridium complexes such as [IrCp ^* (H ₂ O) ₃ ] (BF ₄ ) ₂ ; [RhCp ^* (H ₂ O) ₃ ] (OTf) ₂ , [RhCp ^* (H ₂ O) ₃ ] SO ₄ , rhodium complexes such as [RhCp ^* (H ₂ O) ₃ ] (PF ₆ ) ₂ and [RhCp ^* (H ₂ O) ₃ ] (BF ₄ ) ₂ ; [RuCp ^* (CH ₃ CN) ₃ ] PF ₆ , Ruthenium complexes such as [Ru (η ⁶ -p-cym) (H ₂ O) ₃ ] (PF ₆ ) ₂ and [Ru (η ⁶ -HMB) (H ₂ O) ₃ ] (OTf) _2. Be done. In the above formula, Cp ^* represents a tetramethylcyclopentadienyl ligand, η ⁶ -p-cym represents cymene, and HMB represents hexamethylbenzene.

  In the mesoporous organic silica having the structure represented by the formula (1a), if the structure represented by the formula (1a) is arranged on the inner surface of the pores (pore wall) of the mesoporous organic silica, It may be arranged on the outer surface, or may be contained in the skeleton of the mesoporous organic silica (hereinafter, this mesoporous organic silica is also referred to as “first mesoporous organic silica”), or a normal mesoporous It may be bonded to the inner surface (pore wall) of the pores of silica (hereinafter, this mesoporous organic silica is also referred to as “second mesoporous organic silica”).

Further, as described above, R ^{1 to} R ⁸ in the formula (1a) are the same groups as R ^{1 to} R ⁸ in the formula (1). R ^b in the formula (2) in the formula (1a) is preferably a hydrogen atom from the viewpoint of suppressing steric hindrance. In addition, as the adjacent structure bonded to the binding site * in the formula (2) in the formula (1a), a repeating unit having the structure represented by the formula (1a) in the mesoporous organic silica, the formula Examples thereof include the structure represented by (3) and the structure represented by the above formula (4).

  In the mesoporous organic silica having the structure represented by the formula (1a), the proportion of the structure represented by the formula (1a) is not particularly limited as long as it is 1% by mass or more. From the viewpoint that the content of the metal complex coordinated to the transition metal atom is increased and the catalytic activity is improved, the first mesoporous organic silica is preferably 1 to 90% by mass, and 1 to 75% by mass. More preferably, 1.5 to 60% by mass is further preferable, 2.5 to 45% by mass is particularly preferable, 3.0 to 30% by mass is most preferable, and the second mesoporous organic silica is 1 to 60% by mass. % Is more preferable, 1.5 to 50% by mass is more preferable, 2.0 to 40% by mass is further preferable, and 2.5 to 35% by mass is particularly preferable.

  When the ratio of the structure represented by the formula (1a) is less than 100% by mass, the structure other than the structure represented by the formula (1a) (hereinafter, referred to as “other structure”) is represented by the formula (3). ) And (4) are preferable, and any one of these structures may be contained or both of them may be contained.

  In the mesoporous organic silica having the structure represented by the formula (1a), the proportion of such other structure is 99% by mass or less with respect to the total amount with the structure represented by the formula (1a). It is not particularly limited as long as it is, but from the viewpoint of improving the durability of the catalyst, the first transition metal-containing mesoporous organic silica is preferably 10 to 99% by mass, more preferably 25 to 99% by mass, 40-98.5 mass% is more preferable, 55-97.5 mass% is especially preferable, 70-97.0 mass% is the most preferable, and the second transition metal-containing mesoporous organic silica is 40-99 mass%. %, More preferably 50 to 98.5% by mass, further preferably 60 to 98.0% by mass, and particularly preferably 65 to 97.5% by mass.

<Method for producing carbonyl compound>
Next, the method for producing the carbonyl compound of the present invention will be described. The method for producing a carbonyl compound of the present invention is a method of producing a carbonyl compound by dehydrogenating alcohols using the solid catalyst of the present invention.

  The alcohol used as a raw material is not particularly limited, and examples thereof include primary alcohols such as methanol, ethanol, 1-propanol, 1-octanol, benzyl alcohol, 4-methoxybenzyl alcohol, 4-bromobenzyl alcohol, and cyclohexanemethanol. 1-phenylethanol, 1- (4-methoxyphenyl) ethanol, 1- (2-methoxyphenyl) ethanol, 1- (4-tert-butylphenyl) ethanol, 1- (4-chlorophenyl) ethanol, 1- ( 4-bromophenyl) ethanol, 1- [4- (trifluoromethyl) phenyl] ethanol, 1- (4-cyanophenyl) ethanol, 1-phenyl-1-propanol, 2-propanol, 2-octanol, 6-undecanol , Cyclo Hexanol, include secondary alcohols such as cyclopentanol.

  In the method for producing a carbonyl compound of the present invention, the dehydrogenation reaction of alcohols may be carried out without solvent or in a solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, oxygen-containing solvents such as tetrahydrofuran and diisopropyl ether, and halogen solvents such as dichloromethane. , A nitrogen-containing solvent such as dimethylformamide, an alcohol solvent such as t-butanol, and water. The temperature for the dehydrogenation reaction of alcohols is preferably 25 to 250 ° C, more preferably 50 to 180 ° C.

  The carbonyl compound thus obtained is, for example, an aldehyde when a primary alcohol is used as a raw material and a ketone when a secondary alcohol is used as a raw material. Further, after dehydrogenating a primary alcohol to produce an aldehyde, hydrating this aldehyde to produce a hemiacetal, and further dehydrogenating this hemiacetal to produce a carboxylic acid. You can also

<Method of producing hydrogen>
Next, the method for producing hydrogen of the present invention will be described. The method for producing hydrogen of the present invention is a method of dehydrogenating at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate salts using the solid catalyst of the present invention to generate hydrogen. Is.

  The alcohol used as a raw material is not particularly limited, but from the viewpoint of high hydrogen generation efficiency, the above primary alcohol is preferable, and a mixed solution of the above primary alcohol and water is more preferable. The formate salt is not particularly limited, and examples thereof include alkali metal salts of formic acid such as sodium formate and potassium formate; ammonium formate salts.

  In the method for producing hydrogen of the present invention, the dehydrogenation reaction of the oxygen-containing compound may be carried out without solvent or in a solvent. As the solvent, the solvent exemplified in the method for producing a carbonyl compound of the present invention can be used. Moreover, in the method for producing hydrogen of the present invention, the dehydrogenation reaction of the oxygen-containing compound may be carried out in a gas phase. By carrying out the dehydrogenation reaction of the oxygen-containing compound in the gas phase, even if carbon dioxide is produced as a by-product, it can be easily discharged out of the reaction system, and the reaction system does not become acidic, so a base It becomes possible to continuously produce hydrogen without adding.

  The temperature of the dehydrogenation reaction in the method for producing hydrogen of the present invention is preferably 50 to 280 ° C, more preferably 80 to 180 ° C.

  Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Preparation Example A1)
<Preparation of bis (methoxymethoxy) diiodobipyridine>
In a 100 ml two-necked flask equipped with a stir bar under an argon atmosphere, 6,6′-dihydroxy-2,2′-bipyridine (HO-BPy-OH, 1.0 g, 5.36 mmol), iodine (2.84 g) , 11.2 mmol) and potassium carbonate (5.88 g, 42.6 mmol) were weighed, and degassed distilled water (20 ml) and dehydrated 1,4-dioxane (8 ml) were added. The resulting mixture was vigorously stirred at room temperature for 4 days, and the following reaction formula (P1):

The reaction represented by Distilled water (20 ml) and ethyl acetate (40 ml) were added to the obtained reaction product, and the formed yellow solid precipitate was collected by filtration. The precipitate was washed with distilled water (20 ml) and ethyl acetate (20 ml) and then dried under reduced pressure to give a yellow powder (yield: 1.94 g). The yellow powder was used in the following synthesis reaction as it was without purification, that is, as a crude product. The yellow powder was identified by ¹ H-NMR measurement and was 6,6′-dihydroxy-5,5′-diiodo-2,2′-bipyridine (I- (HO) BPy (OH) -I). It was confirmed. The results are shown below.
¹ H-NMR (400 MHz, DMSO-d ⁶ ): δ 7.89 (d, 2H), 6.53 (d, 2H).

  Next, under an argon atmosphere, in a 100 ml two-necked flask equipped with a stirrer, the crude product of I- (HO) BPy (OH) -I (1.94 g) and potassium carbonate (1.89 g, 13.7 mmol). ) Was weighed, and dehydrated tetrahydrofuran (THF, 30 ml) was further added. Chloromethyl methyl ether (MOMCl, 790 mg, 9.8 mmol) was added to the obtained mixture, and the mixture was stirred at room temperature for 21 hr, then the following reaction formula (P2):

The reaction represented by After completion of the reaction, the solvent was distilled off under reduced pressure, dichloromethane was added to the obtained solid component to dissolve it, and the undissolved component was removed by Celite filtration. Then, the solvent was distilled off again under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent: dichloromethane = 100) to obtain a white powder (yield: 981 mg, yield: 35%). It was This white powder was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and 6,6′-bis (methoxymethoxy) -5,5′-diiodo-2,2′-bipyridine (I- (MOMO) BPy was used. (OMOM) -I) was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.13 (d, 2H), 7.73 (d, 2H), 5.68 (s, 4H), 3.59 (s, 6H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ159.85, 152.52, 149.40, 116.40, 92.72, 81.03, 57.53.

(Preparation example B1)
<Preparation of organosilane compound containing bipyridine group>
Under an argon atmosphere, the I- (MOMO) BPy (OMOM) -I (99.8 mg, 0.19 mmol) obtained in Preparation Example A1 and diacetonitrile (1,5) were placed in a two-neck glass tube equipped with a stir bar. - cyclooctadiene) rhodium (I) tetrafluoroborate _{([Rh (cod) (CH} 3 CN) 2] BF 4, 4.1mg, 0.01mmol) and tetrabutylammonium iodide _(n-Bu 4 NI, 141.8 mg, 0.38 mmol) was weighed, and further dehydrated dimethylformamide (DMF, 1 ml) and dehydrated triethylamine (Et ₃ N, 400 μl, 0.29 mmol) were added. After cooling the two-necked glass tube to 0 ° C., triethoxysilane ((EtO) ₃ SiH, 350 μl, 1.9 mmol) was added, and the obtained mixture was stirred at 80 ° C. for 24 hours, and the reaction formula below was used. (P3):

The reaction represented by After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to silica gel column chromatography (first developing solvent: hexane / ethyl acetate = 3/2, second developing solvent: hexane / ethyl acetate = It was purified twice by (3/1) to obtain a colorless transparent liquid (yield: 20.4 mg, yield: 18%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and 6,6′-bis (methoxymethoxy) -5,5′-bis (triethoxysilyl) -2,2′-bipyridine was identified. (Si- (MOMO) BPy (OMOM) -Si) was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.09 (d, 2H), 7.99 (d, 2H), 5.70 (s, 4H), 3.92 (q, 12H), 3.58. (S, 6H), 1.26 (t, 18H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ165.63, 155.21, 148.73, 114.49, 114.01, 91.57, 58.84, 57.28, 18.20.

(Preparation Example C1)
<Preparation of mesoporous organic silica having a hydroxyl group-containing bipyridine group>
In a 110 ml vial tube equipped with a stir bar, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₂ H ₂₇ (OCH ₂ CH ₂ ) ₁₀ OH, 920 mg, 1.29 mmol) and sodium chloride (3.30 g). , 56.5 mmol) was weighed, and distilled water (34.3 ml) and concentrated hydrochloric acid (2.26 ml) were further added. The resulting mixture was stirred at 50 ° C. for 1 hour to completely dissolve the nonionic surfactant. While vigorously stirring the obtained aqueous surfactant solution, the Si- (MOMO) BPy (OMOM) -Si (395 mg, 0.66 mmol) and 4,4'-bis (obtained in Preparation Example B1 were added thereto. An ethanol solution (0.5 ml) of triethoxysilyl) biphenyl (Si-BPh-Si, 1.26 g, 2.63 mmol) was added dropwise over 1 minute. The obtained solution was stirred at 60 ° C. for 24 hours, and further left to stand for 24 hours while being heated at 80 ° C. to obtain the following reaction formula (P4):

The reaction represented by The produced pale yellow precipitate was collected by pressure filtration to obtain a bipyridine group- and biphenyl group-containing organic silica mesostructure containing a template surfactant (Brij76). This organosilica mesostructure was added to acidic ethanol (a mixed solution of 265 ml of ethanol and 7.5 ml of 2M hydrochloric acid) and suspended overnight to remove the template surfactant, thereby removing a light yellow hydroxyl group-containing bipyridine group. A mesoporous organic silica powder having ((HO) BPy (OH) -BPh-PMO, yield: 1.02 g) was obtained.

The X-ray diffraction pattern of this (HO) BPy (OH) -BPh-PMO was measured using a powder X-ray diffractometer ("RINT-TTR" manufactured by Rigaku Corporation) with Cu-Kα as the X-ray source and a current value. When measured under the conditions of 50 mA and a voltage value of 300 mV, as shown in FIG. 1A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.40 ° (d = 6.30 nm). Further, the nitrogen adsorption / desorption isotherm of the (HO) BPy (OH) -BPh-PMO was measured using a specific surface area / pore distribution measuring device ("Nova3000e" manufactured by Cantachrome Co., Ltd.), and is shown in FIG. 1B. So it was type IV. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, it was confirmed that the (HO) BPy (OH) -BPh-PMO had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of the (HO) BPy (OH) -BPh-PMO was calculated by the BET (Brunauer-Emmett-Teller) method (P / P ₀ = 0). It was 844 m < ² > / g when calculated in the range of 0.1 to 0.2), and when the central pore diameter d _DFT was calculated by the DFT (Density-Functional-Theory) method, it was 4.2 nm, which was a total fineness. The pore volume V _P was calculated by the t-plot method (calculated in the range of P / P ₀ = 0.6 to 0.8) and found to be 0.48 cm ³ / g.

(Preparation Example B2)
<Preparation of organosilane compound containing bipyridine group>
Under an argon atmosphere, a tetrahydrofuran (THF) solution (4.7 ml) of isopropylmagnesium chloride (i-PrMgCl, 4.73 mmol) was placed in a 30 ml two-necked eggplant flask equipped with a stir bar and cooled to -15 ° C. The above-mentioned I- (MOMO) BPy (OMOM) -I (500 mg, 0.95 mmol) obtained in Preparation Example A1 was added thereto and stirred for 30 minutes, and further stirred at -10 ° C for 3 hours. Allyl bromide (1.2 ml, 14.2 mmol) was added dropwise to the obtained mixture, and the mixture was stirred at room temperature for 4 hr to give the following reaction formula (P5):

The reaction represented by After quenching with aqueous ammonia to terminate the reaction, the produced emulsion was removed by Celite filtration. The obtained reaction product was extracted with diethyl ether, dried over anhydrous sodium sulfate, and then the solvent was removed using a rotary evaporator. The obtained crude product was isolated and purified by column chromatography (developing solvent: dichloromethane) to obtain a white powder (yield: 272.4 mg, yield: 82%). This white powder was identified by ¹ H-NMR measurement, and 6,6′-bis (methoxymethoxy) -5,5′-diallyl-2,2′-bipyridine (Allyl- (MOMO) BPy (OMOM) -Allyl) was identified. Was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CD ₃ OD, rt): δ 7.91 (d, 2H), 7.52 (d, 2H), 6.01 (m, 2H), 5.70 (s, 4H). ), 5.10 (m, 4H), 3.55 (s, 6H), 3.41 (m, 4H).

Then, under an argon atmosphere, tris (triphenylphosphine) rhodium (I) chloride ([RhCl (PPh ₃ ) ₃ ], 15.8 mg, 0.0086 mmol) and tris were added to a 5 ml two-necked test tube equipped with a stir bar. Ethoxysilane ((EtO) ₃ SiH, 702 μl, 4.28 mmol) was added, and the mixture was stirred at 80 ° C. The above-mentioned Allyl- (MOMO) BPy (OMOM) -Allyl (299.9 mg, 0.86 mmol) was added to the obtained mixture, and the mixture was stirred at 80 ° C for 20 hours, and the following reaction formula (P6):

The reaction represented by After passing the obtained reaction product through a short silica gel column (developing solvent: hexane / ethyl acetate = 7/1), the solvent was removed using a rotary evaporator. The obtained crude product was isolated and purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 7/1) to obtain a colorless transparent liquid (yield: 515.5 mg, yield: 88%). .. This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and 6,6′-bis (methoxymethoxy) -5,5′-bis (3- (triethoxysilyl) propyl) -2 was identified. , 2'-bipyridine (Si-C3- (MOMO) BPy (OMOM) -C3-Si). The results are shown below.
¹ H-NMR (400 MHz, CD ₃ OD, rt): δ 7.87 (d, 2H), 7.49 (d, 2H), 5.69 (s, 4H), 3.81 (q, 12H). ), 3.58 (s, 6H), 2.67 (t, 4H), 1.76 (m, 4H), 1.21 (t, 18H), 0.69 (t, 4H).
¹³ C-NMR (400 MHz, CD ₃ OD, rt): δ159.7, 150.9, 139.4, 124.8, 114.3, 91.6, 58.4, 57.3, 33. 2,22.6,18.4,10.3.

(Preparation Example C2)
<Preparation of mesoporous silica having a hydroxyl group-containing bipyridine group>
Under an argon atmosphere, mesoporous silica FSM-16 (manufactured by Taiyo Kagaku Co., Ltd., 2.0 g) was weighed into a 200 ml three-necked flask equipped with a stirrer and a reflux tube, and toluene (80 ml) was further added. A toluene solution (20 ml) of the Si-C3- (MOMO) BPy (OMOM) -C3-Si (800 mg, 1.17 mmol) obtained in Preparation Example B2 was added to the obtained dispersion liquid, and trifluoroacetic acid was further added. (0.066 ml) was added dropwise. The resulting mixture was stirred at 120 ° C. for 24 hours, and the following reaction formula (P7):

The reaction represented by After completion of the reaction, the obtained solid component was collected by filtration and washed with toluene and ethanol. The solid component after washing was dried under vacuum, added to 2M hydrochloric acid (50 ml), and stirred at 50 ° C for 2 hours. Then, it cooled to room temperature and collected the solid component by filtration. The obtained solid component was washed with ethanol and water, and then dried at 50 ° C. under vacuum to obtain a mesoporous silica powder (C3- (HO) BPy (OH) -C3-FSM16 having a pale yellow hydroxyl group-containing bipyridine group. , Yield: 2.47 g) was obtained.

The X-ray diffraction pattern of this C3- (HO) BPy (OH) -C3-FSM16 was measured in the same manner as in Preparation Example C1, and as shown in FIG. 2A, 2θ = 1.88 ° (d = 4.70 nm ), A diffraction peak derived from a regular mesostructure was observed. Further, when the nitrogen adsorption / desorption isotherm of the C3- (HO) BPy (OH) -C3-FSM16 was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 2B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption-desorption isotherm, it was confirmed that the C3- (HO) BPy (OH) -C3-FSM16 had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of the C3- (HO) BPy (OH) -C3-FSM16 was calculated in the same manner as in Preparation Example C1, and found to be 705 m ² / g The central pore diameter d _DFT was calculated to be 4.3 nm, and the total pore volume V _P was calculated to be 0.54 cm ³ / g.

(Preparation Example B3)
<Preparation of organosilane compound containing bipyridine group>
Under an argon atmosphere, in a 100 ml two-necked eggplant flask equipped with a reflux tube, the I- (MOMO) BPy (OMOM) -I (1.0 g, 1.89 mmol) obtained in Preparation Example A1 and palladium (II) acetate were prepared. (Pd (OAc) ₂ , 8.6 mg, 0.04 mmol), triphenylphosphine (PPh ₃ , 30.0 mg, 0.11 mmol), cesium carbonate (1.85 g, 5.68 mmol), potassium vinyl trifluoroborate ( 761.3 mg, 5.68 mmol), tetrahydrofuran (THF, 29.0 ml) and distilled water (1.0 ml) were added, and further a stir bar was added. The resulting mixture was stirred at 85 ° C. for 48 hours, and the following reaction formula (P8):

The reaction represented by After completion of the reaction, the solvent was removed using a rotary evaporator, and distilled water (5 ml) was added to the obtained residue. The obtained aqueous solution was transferred to a separatory funnel and subjected to liquid separation extraction three times with dichloromethane (30 ml × 3 times). The obtained organic layers were put together in a separatory funnel and washed with distilled water (10 ml). The organic layer was dried with sodium sulfate and then filtered. The solvent of the resulting yellow solution was removed using a rotary evaporator. The obtained residue was passed through a short silica gel column (developing solvent: hexane / ethyl acetate = 4/1), and then the solvent was distilled off to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 4/1) to obtain a white solid (yield: 382.7 mg, yield: 62%). This white solid was identified by ¹ H-NMR measurement, and 6,6′-bis (methoxymethoxy) -5,5′-divinyl-2,2′-bipyridine (Vinyl- (MOMO) BPy (OMOM) -Vinyl). Was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , rt): δ 7.97 (d, 2H), 7.83 (d, 2H), 6.98 (q, 2H), 5.89 (dd, 2H). , 5.74 (s, 4H), 5.40 (dd, 2H), 3.58 (s, 6H).

Next, under an argon atmosphere, the above Vinyl- (MOMO) BPy (OMOM) -Vinyl (500 mg, 1.52 mmol), toluene (6.2 ml), 1,3-divinyl-1,1 were placed in a 30 ml two-necked eggplant flask. , 3,3-Tetramethyldisiloxane platinum (0) complex solution (Karstedt catalyst, ~ 2% Pt xylene solution, 175.0 μl, 0.02 mmol-Pt), triethoxysilane ((EtO) ₃ SiH, 1.15 ml) , 6.23 mmol) and a stirrer. The resulting yellowish brown solution was stirred at 100 ° C. for 20 hours with stirring, and the following reaction formula (P9):

The reaction represented by The obtained reaction solution was filtered with a filter paper, and the solvent of the obtained filtrate was removed using a rotary evaporator. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 5/1) to obtain a colorless transparent liquid (yield: 345.8 mg, yield: 35%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 6,6′-bis (methoxymethoxy) -5,5′-bis (2- (triethoxysilyl) ethyl) -2. , 2'-bipyridine (Si-C2- (MOMO) BPy (OMOM) -C2-Si). The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , rt): δ 7.89 (d, 2H), 7.55 (d, 2H), 5.71 (s, 4H), 3.86 (q, 12H). , 3.57 (s, 6H), 2.75 (m, 4H), 1.26 (t, 18H), 1.01 (m, 4H).
¹³ C-NMR (400 MHz, CDCl ₃ , rt): δ159.4, 150.8, 138.3, 127.0, 114.4, 91.6, 58.5, 57.3, 23.3. , 18.4, 10.2.

(Preparation Example C3)
<Preparation of mesoporous silica having a hydroxyl group-containing bipyridine group>
Under an argon atmosphere, mesoporous silica FSM-16 (manufactured by Taiyo Kagaku Co., Ltd., 1.0 g) was weighed in a 200 ml three-necked flask equipped with a stirrer and a reflux tube, and toluene (40 ml) was further added. To the obtained dispersion liquid was added the toluene solution (10 ml) of Si-C2- (MOMO) BPy (OMOM) -C2-Si (382 mg, 0.58 mmol) obtained in Preparation Example B3, and trifluoroacetic acid was further added. (0.033 ml) was added dropwise. The resulting mixture was stirred at 120 ° C. for 24 hours, and the following reaction formula (P10):

The reaction represented by After completion of the reaction, the obtained solid component was collected by filtration and washed with toluene and ethanol. The solid component after washing was dried under vacuum, added to 2M hydrochloric acid (30 ml), and stirred at 50 ° C for 2 hours. Then, it cooled to room temperature and collected the solid component by filtration. The obtained solid component is washed with ethanol and water, and then dried under vacuum at 50 ° C. to obtain a mesoporous silica powder (C2- (HO) BPy (OH) -C2-FSM16 having a pale yellow hydroxyl group-containing bipyridine group. , Yield: 1.00 g) was obtained.

The X-ray diffraction pattern of this C2- (HO) BPy (OH) -C2-FSM16 was measured in the same manner as in Preparation Example C1, and as shown in FIG. 3A, 2θ = 1.80 ° (d = 4.65 nm ), A diffraction peak derived from a regular mesostructure was observed. Further, the nitrogen adsorption-desorption isotherm of the C2- (HO) BPy (OH) -C2-FSM16 was measured in the same manner as in Preparation Example C1, and as a result, it was IV type as shown in FIG. 3B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, it was confirmed that the C2- (HO) BPy (OH) -C2-FSM16 had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of the C2- (HO) BPy (OH) -C2-FSM16 was calculated in the same manner as in Preparation Example C1, and found to be 709 m ² / g The central pore diameter d _DFT was calculated to be 4.3 nm, and the total pore volume V _P was calculated to be 0.53 cm ³ / g.

(Preparation Example C4)
<Preparation of mesoporous organic silica having a hydroxyl group-containing bipyridine group>
In a 110 ml vial tube equipped with a stir bar, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₂ H ₂₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.0 g, 1.41 mmol) and sodium chloride (3 0.0 g, 51.3 mmol) was weighed, and distilled water (52.0 ml) and concentrated hydrochloric acid (3.46 ml) were further added. The resulting mixture was stirred at 60 ° C. for 2 hours to completely dissolve the nonionic surfactant. While vigorously stirring the obtained surfactant aqueous solution, the Si-C3- (MOMO) BPy (OMOM) -C3-Si (458 mg, 0.67 mmol) and 1,2 obtained in Preparation Example B2 were added thereto. An ethanol solution (1.0 ml) of -bis (triethoxysilyl) ethane (Si-Et-Si, 1.35 g, 3.81 mmol) was added dropwise. The obtained solution was stirred at 60 ° C. for 24 hours, and further left standing for 24 hours while being heated at 80 ° C. to obtain the following reaction formula (P11):

The reaction represented by The generated pale yellow precipitate was collected by pressure filtration to obtain a bipyridine group-containing organic silica mesostructure containing a template surfactant (Brij76). The organosilica mesostructure was added to acidic ethanol (a mixed solution of 100 ml of ethanol and 3.0 ml of 2N hydrochloric acid) and suspended overnight to remove the template surfactant, thereby removing a pale yellow hydroxyl group-containing bipyridine group. A mesoporous organic silica powder having (C3- (HO) BPy (OH) -C3-Et-PMO, yield: 0.904 g) was obtained.

The X-ray diffraction pattern of this C3- (HO) BPy (OH) -C3-Et-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 4A, 2θ = 1.36 ° (d = 6 A diffraction peak derived from a regular mesostructure was observed at 0.50 nm), 2.36 ° (d = 3.75 nm) and 2.72 ° (d = 3.25 nm). Further, the nitrogen adsorption-desorption isotherm of C3- (HO) BPy (OH) -C3-Et-PMO was measured in the same manner as in Preparation Example C1, and it was IV type as shown in FIG. 4B. Therefore, it was confirmed from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm that the C3- (HO) BPy (OH) -C3-Et-PMO had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of the C3- (HO) BPy (OH) -C3-Et-PMO was calculated in the same manner as in Preparation Example C1, and found to be 773 m ^2. The central pore diameter d _DFT was calculated to be 4.4 nm, and the total pore volume V _P was calculated to be 0.58 cm ³ / g.

(Synthesis example 1)
<Synthesis of Mesoporous Organosilica Having Hydroxyl Group-Containing Bipyridine Group Coordinated to Ir>
In a brown 110 ml vial tube equipped with a stirrer, the mesoporous organic silica powder (HO) BPy (OH) -BPh-PMO (600 mg) having a hydroxyl group-containing bipyridine group obtained in Preparation Example C1 was weighed and further distilled. Water (40 ml) was added. While stirring the resulting dispersion, an iridium complex [IrCp ^* (H ₂ O) ₃ ] (OTf) prepared according to the method described in Organometallics, 1999, 18 (26), pp5470-5474 was added thereto ^. ₂ (in the above formula, Cp ^* represents a tetramethylcyclopentadienyl ligand. 120 mg, 0.18 mmol) in water (20 ml) was added dropwise. The obtained mixture was stirred at 80 ° C. for 20 hours to give the following reaction formula (S1):

The reaction represented by After completion of the reaction, the mixture was cooled to room temperature and filtered with a membrane filter to collect solid components. The obtained solid component was washed with distilled water (30 ml), redispersed in ethanol (30 ml), and collected by filtration. This redispersion / filtration operation was repeated 3 times to remove the unreacted iridium precursor, and then the solid component was dried under reduced pressure to obtain a mesoporous hydroxyl group-containing bipyridine group coordinated to light brown Ir. An organic silica powder (Ir- (HO) BPy (OH) -BPh-PMO, yield: 600 mg) was obtained.

The X-ray diffraction pattern of this Ir- (HO) BPy (OH) -BPh-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 5A, 2θ = 1.36 ° (d = 6.50 nm ), A diffraction peak derived from a regular mesostructure was observed. Further, when the nitrogen adsorption / desorption isotherm of Ir- (HO) BPy (OH) -BPh-PMO was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 5B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the Ir- (HO) BPy (OH) -BPh-PMO had regular and uniform mesopores, and was obtained in Preparation Example C1. It was confirmed that the regular and uniform mesopore structure was maintained even when Ir was immobilized on (HO) BPy (OH) -BPh-PMO. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of Ir- (HO) BPy (OH) -BPh-PMO was calculated in the same manner as in Preparation Example C1, and was 673 m ² / g The central pore diameter d _DFT was calculated to be 4.4 nm, and the total pore volume V _P was calculated to be 0.41 cm ³ / g. In addition, the Ir content in the Ir- (HO) BPy (OH) -BPh-PMO was measured by ICP emission spectroscopy (ICP-AES analysis, carried out by Toray Research Center Co., Ltd.). It was -0.255 mmol-Ir / g.

(Synthesis example 2)
<Synthesis of mesoporous organic silica having a bipyridone group coordinated to Ir>
Mesoporous organic silica powder Ir- (HO) BPy (OH) -BPh-PMO (0.255mmol-Ir) having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 was placed in a reaction vessel equipped with a stirring bar. / G, 183 mg, 46.7 μmol) was weighed, and an aqueous solution of methanol (11.25 ml) containing NaOH (16 mg, 0.40 mmol) was further added. The obtained dispersion liquid was stirred at room temperature for 1 hour, and the following reaction formula (S2):

The reaction represented by After the reaction was completed, the solid component was collected by filtration with a membrane filter. The obtained solid component was dried under reduced pressure to obtain a mesoporous organic silica powder having a light brown Ir-coordinated bipyridone group (Ir-BPyd-BPh-PMO, yield: 180 mg). The bipyridone group coordinated to Ir is a tautomer of the bipyridine group having a hydroxyl group coordinated to Ir.

An X-ray diffraction pattern of this Ir-BPyd-BPh-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 6A, a regular meso at 2θ = 1.36 ° (d = 6.50 nm) was obtained. A diffraction peak derived from the structure was observed. Further, when the nitrogen adsorption / desorption isotherm of Ir-BPyd-BPh-PMO was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 6B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the Ir-BPyd-BPh-PMO had regular and uniform mesopores, and Ir- (HO) BPy obtained in Synthesis Example 1 was obtained. It was confirmed that the regular and uniform mesopore structure was maintained even when (OH) -BPh-PMO was treated with NaOH. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of Ir-BPyd-BPh-PMO was calculated in the same manner as in Preparation Example C1, and was 649 m ² / g, and the central pore The calculated diameter d _DFT was 4.1 nm, and the calculated total pore volume V _P was 0.40 cm ³ / g. In addition, the Ir content in the Ir-BPyd-BPh-PMO was measured using a scanning electron microscope (“S-5500” manufactured by Hitachi High-Technologies Corporation) equipped with an energy dispersive X-ray spectroscopic analyzer. When measured by an analytical method, it was 0.198 mmol-Ir / g.

(Synthesis example 3)
<Synthesis of mesoporous silica having a hydroxyl group-containing bipyridine group coordinated to Ir>
In a brown 110 ml vial tube equipped with a stirrer, mesoporous silica powder C3- (HO) BPy (OH) -C3-FSM16 (600 mg) having a hydroxyl group-containing bipyridine group obtained in Preparation Example C2 was weighed, and further, Distilled water (33.6 ml) was added. While stirring the resulting dispersion, an iridium complex [IrCp ^* (H ₂ O) ₃ ] (OTf) prepared according to the method described in Organometallics, 1999, 18 (26), pp5470-5474 was added thereto ^. ₂ (in the above formula, Cp ^* represents a tetramethylcyclopentadienyl ligand. 102 mg, 0.15 mmol) in water (16.8 ml) was added dropwise. The resulting mixture was stirred at 80 ° C. for 20 hours, and the following reaction formula (S3):

The reaction represented by After completion of the reaction, solid components were collected by filtration. The obtained solid component was washed with ethanol and then dried under vacuum to obtain a mesoporous silica powder having a brown Ir-coordinated hydroxyl group-containing bipyridine group (Ir-C3- (HO) BPy (OH) -C3-. FSM16, yield: 600 mg) was obtained.

The X-ray diffraction pattern of this Ir-C3- (HO) BPy (OH) -C3-FSM16 was measured in the same manner as in Preparation Example C1, and as shown in FIG. 7A, 2θ = 1.94 ° (d = 4 A diffraction peak derived from a regular mesostructure was observed at 0.55 nm. Moreover, when the nitrogen adsorption / desorption isotherm of Ir-C3- (HO) BPy (OH) -C3-FSM16 was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 7B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the Ir-C3- (HO) BPy (OH) -C3-FSM16 had regular and uniform mesopores, and was obtained in Preparation Example C2. It was confirmed that even if Ir was immobilized on the obtained C3- (HO) BPy (OH) -C3-FSM16, a regular and uniform mesopore structure was maintained. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of Ir-C3- (HO) BPy (OH) -C3-FSM16 was calculated in the same manner as in Preparation Example C1, and found to be 641 m ^2. The central pore diameter d _DFT was calculated to be 3.8 nm, and the total pore volume V _P was calculated to be 0.46 cm ³ / g. Moreover, when the Ir content in the Ir-C3- (HO) BPy (OH) -C3-FSM16 was measured by the ICP-AES analysis method in the same manner as in Synthesis Example 1, it was 0.228 mmol-Ir / g. It was

(Synthesis example 4)
<Synthesis of mesoporous silica having a bipyridone group coordinated to Ir>
In a brown 50 ml vial tube equipped with a stirrer, mesoporous silica powder Ir-C3- (HO) BPy (OH) -C3-FSM16 (0 having the hydroxyl group-containing bipyridine group obtained in Synthesis Example 3 was obtained. 0.228 mmol-Ir / g, 200 mg, 45.8 μmol) was weighed, and an aqueous solution of methanol (11.25 ml) containing NaOH (16 mg, 0.40 mmol) was further added. The obtained dispersion liquid was stirred at room temperature for 1 hour, and the following reaction formula (S4):

The reaction represented by After the reaction was completed, the solid component was collected by filtration with a membrane filter. The obtained solid component was dried under reduced pressure to obtain a mesoporous silica powder having a light brown Ir-coordinated bipyridone group (Ir-C3-BPyd-C3-FSM16, yield: 180 mg). The bipyridone group coordinated to Ir is a tautomer of the bipyridine group having a hydroxyl group coordinated to Ir.

The X-ray diffraction pattern of this Ir-C3-BPyd-C3-FSM16 was measured in the same manner as in Preparation Example C1, and as shown in FIG. 8A, it was regular at 2θ = 1.90 ° (d = 4.65 nm). A diffraction peak derived from a different mesostructure was observed. Moreover, when the nitrogen adsorption / desorption isotherm of Ir-C3-BPyd-C3-FSM16 was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 8B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the Ir-C3-BPyd-C3-FSM16 had regular and uniform mesopores, and the Ir-C3-obtained in Synthesis Example 3 was obtained. It was confirmed that even if the (HO) BPy (OH) -C3-FSM16 was treated with NaOH, the regular and uniform mesopore structure was maintained. Furthermore, when the specific surface area S _BET of Ir-C3-BPyd-C3-FSM16 was calculated based on the obtained nitrogen adsorption / desorption isotherm in the same manner as in Preparation Example C1, it was 593 m ² / g, and The pore diameter d _DFT was calculated to be 4.1 nm, and the total pore volume V _P was calculated to be 0.42 cm ³ / g. The Ir content in Ir-C3-BPyd-C3-FSM16 was 0.228 mmol-Ir / g when measured by SEM-EDX analysis in the same manner as in Synthesis Example 2.

(Synthesis example 5)
<Synthesis of mesoporous silica having a hydroxyl group-containing bipyridine group coordinated to Ir>
In a brown 110 ml vial tube equipped with a stirrer, the mesoporous silica powder C2- (HO) BPy (OH) -C2-FSM16 (1.0 g) having a hydroxyl group-containing bipyridine group obtained in Preparation Example C3 was weighed, Further, distilled water (56.0 ml) was added. While stirring the resulting dispersion, an iridium complex [IrCp ^* (H ₂ O) ₃ ] (OTf) prepared according to the method described in Organometallics, 1999, 18 (26), pp5470-5474 was added thereto ^. ₂ (in the above formula, Cp ^* represents a tetramethylcyclopentadienyl ligand. 170 mg, 0.25 mmol) in water (28 ml) was added dropwise. The resulting mixture was stirred at 80 ° C. for 20 hours to give the following reaction formula (S5):

The reaction represented by After completion of the reaction, solid components were collected by filtration. The obtained solid component was washed with ethanol and then dried under vacuum to obtain a mesoporous silica powder (Ir-C2- (HO) BPy (OH) -C2- having a hydroxyl group-containing bipyridine group coordinated to brown Ir. FSM16, yield: 1.0 g) was obtained.

The X-ray diffraction pattern of this Ir-C2- (HO) BPy (OH) -C2-FSM16 was measured in the same manner as in Preparation Example C1, and as shown in FIG. 9A, 2θ = 1.92 ° (d = 4 A diffraction peak derived from a regular mesostructure was observed at (.90 nm). Further, the nitrogen adsorption-desorption isotherm of Ir-C2- (HO) BPy (OH) -C2-FSM16 was measured in the same manner as in Preparation Example C1, and it was IV type as shown in FIG. 9B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption-desorption isotherm, the Ir-C2- (HO) BPy (OH) -C2-FSM16 had regular and uniform mesopores, and was obtained in Preparation Example C3. It was confirmed that even if Ir was immobilized on the obtained C2- (HO) BPy (OH) -C2-FSM16, a regular and uniform mesopore structure was maintained. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of Ir-C2- (HO) BPy (OH) -C2-FSM16 was calculated in the same manner as in Preparation Example C1, and found to be 628 m ^2. The central pore diameter d _DFT was calculated to be 4.1 nm, and the total pore volume V _P was calculated to be 0.46 cm ³ / g. Moreover, when the Ir content in the Ir-C2- (HO) BPy (OH) -C2-FSM16 was measured by the ICP-AES analysis method in the same manner as in Synthesis Example 1, it was 0.223 mmol-Ir / g. It was

(Synthesis example 6)
<Synthesis of Mesoporous Organosilica Having Hydroxyl Group-Containing Bipyridine Group Coordinated to Ir>
A mesoporous organic silica powder C3- (HO) BPy (OH) -C3-Et-PMO (1.5 g) having a hydroxyl group-containing bipyridine group obtained in Preparation Example C4 was weighed into a 200 ml vial tube equipped with a stir bar. Further, distilled water (84.0 ml) was added. While stirring the resulting dispersion, an iridium complex [IrCp ^* (H ₂ O) ₃ ] (OTf) prepared according to the method described in Organometallics, 1999, 18 (26), pp5470-5474 was added thereto ^. An aqueous solution (42 ml) of ₂ (in the above formula, Cp ^* represents a tetramethylcyclopentadienyl ligand. 255 mg, 0.375 mmol) was added dropwise. The obtained mixture was stirred at 80 ° C. for 24 hours, and the following reaction formula (S6):

The reaction represented by After completion of the reaction, solid components were collected by filtration. The obtained solid component was washed with ethanol and then dried under vacuum to obtain a mesoporous organic silica powder having a brown Ir-coordinated hydroxyl group-containing bipyridine group (Ir-C3- (HO) BPy (OH) -C3. -Et-PMO, yield: 1.64 g) was obtained.

The X-ray diffraction pattern of this Ir-C3- (HO) BPy (OH) -C3-Et-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 10A, 2θ = 1.38 ° (d = 6.40 nm), a diffraction peak derived from a regular mesostructure was observed. Further, the nitrogen adsorption-desorption isotherm of Ir-C3- (HO) BPy (OH) -C3-Et-PMO was measured in the same manner as in Preparation Example C1, and it was IV type as shown in FIG. 10B. .. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption-desorption isotherm, the Ir-C3- (HO) BPy (OH) -C3-Et-PMO has regular and uniform mesopores, and Preparation Example C4 It was confirmed that the regular and uniform mesopore structure was maintained even when Ir was immobilized on the C3- (HO) BPy (OH) -C3-Et-PMO obtained in 1. Furthermore, based on the obtained nitrogen adsorption-desorption isotherm, the specific surface area S _BET of Ir-C3- (HO) BPy (OH) -C3-Et-PMO was calculated in the same manner as in Preparation Example C1. 649m was ² / g, was calculated median pore diameter _{d DFT,} is 4.4 nm, was calculated on the total pore volume _{V P,} it was 0.50 cm ³ / g. Further, when the Ir content in the Ir-C3- (HO) BPy (OH) -C3-Et-PMO was measured by the SEM-EDX analysis method in the same manner as in Synthesis Example 2, it was 0.264 mmol-Ir / g. Met.

(Synthesis example 7)
<Synthesis of mesoporous silica having a bipyridone group coordinated to Ir>
In a 50 ml vial tube equipped with a stirrer, mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 6 Ir-C3- (HO) BPy (OH) -C3-Et-PMO ( 0.264 mmol-Ir / g, 200 mg, 52.8 μmol) was weighed, and methanol (10 ml) was added and suspended. After adding a 4M NaOH aqueous solution (100 μl, 0.40 mmol) to the obtained dispersion, the mixture was stirred at room temperature for 15 minutes, and the following reaction formula (S7):

The reaction represented by After the reaction was completed, the solid component was collected by filtration with a membrane filter. The obtained solid component was dried under reduced pressure to obtain a mesoporous organic silica powder having a light brown Ir coordinated bipyridone group (Ir-C3-BPyd-C3-Et-PMO, yield: 205 mg). The bipyridone group coordinated to Ir is a tautomer of the bipyridine group having a hydroxyl group coordinated to Ir.

The X-ray diffraction pattern of this Ir-C3-BPyd-C3-Et-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 11A, it was 2θ = 1.46 ° (d = 6.05 nm). Diffraction peaks derived from a regular mesostructure were observed. Further, when the nitrogen adsorption / desorption isotherm of Ir-C3-BPyd-C3-Et-PMO was measured in the same manner as in Preparation Example C1, it was IV type as shown in FIG. 11B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the Ir-C3-BPyd-C3-Et-PMO had regular and uniform mesopores, and Ir-obtained in Synthesis Example 6 It was confirmed that the regular and uniform mesopore structure was maintained even when C3- (HO) BPy (OH) -C3-Et-PMO was treated with NaOH. Furthermore, when the specific surface area S _BET of Ir-C3-BPyd-C3-Et-PMO was calculated based on the obtained nitrogen adsorption / desorption isotherm in the same manner as in Preparation Example C1, it was 651 m ² / g. The central pore diameter d _DFT was calculated to be 4.4 nm, and the total pore volume V _P was calculated to be 0.49 cm ³ / g. Moreover, when the Ir content in the Ir-C3-BPyd-C3-Et-PMO was measured by the SEM-EDX analysis method in the same manner as in Synthesis Example 2, it was 0.269 mmol-Ir / g.

(Comparative Synthesis Example 1)
<Synthesis of Mesoporous Organic Silica Having Bipyridine Group Coordinated to Ir>
A brown 110 ml vial tube equipped with a stirrer was weighed with bipyridine group-containing mesoporous organic silica powder BPy-PMO (300 mg) prepared according to the method described in JP-A-2015-147911, and acetonitrile (30 ml). Was added. While stirring the obtained dispersion liquid, an iridium complex [IrCp ^* (H ₂ O) ₃ ] (SO ₄ ) (in the above formula) prepared according to the method described in International Publication No. 2011/108730 was added thereto. , Cp ^* represents a tetramethylcyclopentadienyl ligand. 34 mg, 0.071 mmol) in acetonitrile was added dropwise (30 ml). The resulting mixture was stirred at room temperature for 20 hours, and the following reaction formula (S8):

The reaction represented by After completion of the reaction, the mixture was cooled to room temperature and filtered with a membrane filter to collect solid components. The obtained solid component was washed with distilled water (30 ml) and ethanol (30 ml), dried under reduced pressure, and then a mesoporous organic silica powder having a yellow Ir-coordinated bipyridine group (Ir-BPy-PMO, yield) was obtained. : 277 mg) was obtained.

The X-ray diffraction pattern of this Ir-BPy-PMO was measured in the same manner as in Preparation Example C1, and as shown in FIG. 12A, a regular meso structure was formed at 2θ = 1.84 ° (d = 4.80 nm). The derived diffraction peak was observed. In addition, a bipyridine-based layered array structure at 2θ = 7.56 ° (d = 1.17 nm), 2θ = 15.20 ° (d = 0.58 nm), 2θ = 22.9 ° (d = 0.39 nm). A diffraction peak derived from was observed. Further, when the nitrogen adsorption / desorption isotherm of Ir-BPy-PMO was measured in the same manner as in Preparation Example C1, it was found to be type IV as shown in FIG. 12B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, it was confirmed that the Ir-BPy-PMO had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption / desorption isotherm, the specific surface area S _BET of Ir-BPy-PMO was calculated in the same manner as in Preparation Example C1 to find that it was 715 m ² / g and the central pore diameter d. _{When the DFT} was calculated, it was 3.8 nm, and when the total pore volume V _P was calculated, it was 0.47 cm ³ / g. Moreover, when the Ir content in the Ir-BPy-PMO was measured in the same manner as in Synthesis Example 2, it was 0.24 mmol-Ir / g.

(Example 1)
Mesoporous organic silica powder Ir- (HO) BPy (having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst was placed in a two-necked test tube equipped with a stirrer and a reflux tube under an argon atmosphere. OH) -BPh-PMO (0.255 mmol-Ir / g, 4.0 mg, 1.0 μmol-Ir), dehydrated toluene (3 ml) and 1-phenylethanol (122.2 mg, 1 mmol) were weighed. The two-necked test tube was immersed in an oil bath at 150 ° C., heated and refluxed for 20 hours, and the following reaction formula (E1):

The dehydrogenation reaction of 1-phenylethanol represented by After cooling, the Ir- (HO) BPy (OH) -BPh-PMO was collected by filtration using a membrane filter and washed with dehydrated toluene (15 ml). Further, biphenyl was added as an internal standard substance to the obtained filtrate, and the amount of acetophenone produced was measured by gas chromatography (“GC-4000 Plus” manufactured by GL-Sciences, detector: FID) to determine the reaction yield. When calculated, it was 99%.

(Example 2)
A reuse experiment of a solid catalyst was conducted using the Ir- (HO) BPy (OH) -BPh-PMO recovered in Example 1. That is, instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1, the Ir- (HO) BPy (OH) -BPh-PMO recovered in Example 1 was used as a solid catalyst. The dehydrogenation reaction of 1-phenylethanol represented by the above reaction formula (E1) was carried out in the same manner as in Example 1 except that it was used as (1st reuse). Then, in the same manner as in Example 1, the Ir- (HO) BPy (OH) -BPh-PMO was recovered and the amount of acetophenone produced was measured to obtain the reaction yield in the first reuse. In addition, a recycling experiment was performed by repeating these series of operations, and the reaction yield in the second to fourth recycling was determined. As a result, the reaction yield in the first reuse was 100%, the reaction yield in the second reuse was 93%, the reaction yield in the third reuse was 94%, the reaction yield in the fourth reuse was The rate was 90%.

(Example 3)
Mesoporous silica powder Ir having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 5 as a solid catalyst Ir-C2- (HO) BPy (OH) -C2-FSM16 (0.223 mmol-Ir / g, 9. 0 mg, 2.0 μmol-Ir) was used, the temperature of the oil bath was changed to 130 ° C., and the heating reflux time was changed to 6 hours, in the same manner as in Example 1 and the following reaction formula (E2):

The dehydrogenation reaction of 1-phenylethanol represented by and the amount of acetophenone produced was measured, and the reaction yield was determined to be 98%.

(Example 4)
A reuse experiment of a solid catalyst was conducted using the Ir-C2- (HO) BPy (OH) -C2-FSM16 collected in Example 3. That is, instead of the Ir-C2- (HO) BPy (OH) -C2-FSM16 obtained in Synthesis Example 5, the Ir-C2- (HO) BPy (OH) -C2- recovered in Example 3 was used. The dehydrogenation reaction of 1-phenylethanol represented by the reaction formula (E2) was performed in the same manner as in Example 3 except that FSM16 was used as the solid catalyst (this is the first reuse). .. Then, in the same manner as in Example 3, the Ir-C2- (HO) BPy (OH) -C2-FSM16 was recovered and the amount of acetophenone produced was measured to obtain the reaction yield in the first reuse. It was In addition, a recycling experiment was performed by repeating these series of operations, and the reaction yield in the second to fourth recycling was determined. As a result, the reaction yield in the first reuse was 97%, the reaction yield in the second reuse was 97%, the reaction yield in the third reuse was 95%, the reaction yield in the fourth reuse was The rate was 92%.

(Comparative Example 1)
In a two-necked test tube equipped with a stirrer and a reflux tube under an argon atmosphere, J. Am. Chem. Soc. , 2012,134 (8), iridium complex _{^{[IrCp * (dhybpy) (H}} 2 O)] which was prepared according to the method described in pp3643-3646 _{(OTf) 2} (in the formula, Cp ^* is tetramethylcyclopentadienyl Represents a pentadienyl ligand, dhybpy represents a 6,6′-dihydroxy-2,2′-bipyridine ligand, 0.9 mg, 1.0 μmol-Ir), dehydrated toluene (3 ml) and 1-phenyl. Ethanol (122.2 mg, 1 mmol) was weighed. The two-necked test tube was immersed in an oil bath at 140 ° C., heated and refluxed for 20 hours, and the following reaction formula (C1):

The dehydrogenation reaction of 1-phenylethanol represented by After allowing to cool, biphenyl was added to the resulting solution as an internal standard substance, the amount of acetophenone produced was measured by gas chromatography (“GC-4000 Plus” manufactured by GL-Sciences, detector: FID), and the reaction yield was determined. The rate was 5%.

  As shown in FIGS. 13 to 14, in the case of using the solid catalyst of the present invention (Examples 1 to 4), 1-phenylethanol was compared with the case of using the homogeneous catalyst (Comparative Example 1). It was found that acetophenone was obtained in an extremely high yield by the dehydrogenation reaction of. Further, even when the solid catalyst of the present invention was reused (Examples 2 and 4), it was found that the high yield in the dehydrogenation reaction of 1-phenylethanol was maintained and that it could be used repeatedly.

(Example 5)
In a reaction vessel equipped with a stirrer, a mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst Ir- (HO) BPy (OH) -BPh-PMO (0. 249 mmol-Ir / g, 38.6 mg, 9.6 μmol-Ir, 0.048 mmol% -Ir) was weighed, and further methanol (641 mg, 20 mmol), water (1.44 g, 80 mmol) and NaOH (3.2 mg). , 0.08 mmol) was added. After attaching a reflux tube connected to a milligas meter to the reaction vessel, the reaction vessel was immersed in an oil bath at 135 ° C. to give the following reaction formula (E3):

The dehydrogenation reaction of the aqueous methanol solution represented by was continued for 100 hours. The amount of generated gas was measured by a millimeter gas meter, and the components of the generated gas were measured by gas chromatography (“GC-8A” manufactured by Shimadzu Corporation, detector: TCD), and the reaction yield of hydrogen gas was measured. Was 47%.

(Comparative example 2)
Instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1, a mesoporous organic silica powder having a bipyridine group coordinated to Ir obtained in Comparative Synthesis Example 1 Ir-BPy- PMO (0.24 mmol-Ir / g, 40.0 mg, 9.6 μmol-Ir, 0.048 mmol% -Ir) was used as a solid catalyst, and the reaction time was changed to 24 hours in the same manner as in Example 5. , The following reaction formula (C2):

The dehydrogenation reaction of the aqueous methanol solution represented by The amount and components of the generated gas were measured in the same manner as in Example 5, and the reaction yield of hydrogen gas was determined to be less than 1%.

(Example 6)
In a reaction vessel equipped with a stirrer, a mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst Ir- (HO) BPy (OH) -BPh-PMO (0. 255 mmol-Ir / g, 39.2 mg, 10 μmol-Ir) was weighed, and formic acid (921 mg, 20 mmol), water (10 ml) and NaOH (3.2 mg, 0.08 mmol) were added. After attaching a reflux pipe connected to a milligas meter to the reaction vessel, the reaction vessel was immersed in an oil bath at 90 ° C. to give the following reaction formula (E4):

The dehydrogenation reaction of the formic acid aqueous solution represented by the following was continued for 1 hour. The amount of generated gas was measured by a millimeter gas meter, and the components of the generated gas were measured by gas chromatography (“GC-8A” manufactured by Shimadzu Corporation, detector: TCD), and the reaction yield of hydrogen gas was measured. Was 99% or more.

(Example 7)
The following reaction formula (E5) was carried out in the same manner as in Example 6 except that sodium formate (1.36 g, 20 mmol) was used instead of formic acid and the reaction time was changed to 24 hours.

The dehydrogenation reaction of the sodium formate aqueous solution represented by The amount and the components of the generated gas were measured in the same manner as in Example 6, and the reaction yield of hydrogen gas was determined to be 99%.

  As shown in FIG. 15, when a mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir was used as a solid catalyst (Example 5), the mesoporous organic silica having a bipyridine group coordinated to Ir was used. It was found that hydrogen gas can be obtained in a higher yield by the dehydrogenation reaction of the aqueous methanol solution as compared with the case of using the powder (Comparative Example 2). It was also found that hydrogen gas can be obtained in an extremely high yield by dehydrogenating the aqueous formic acid solution (Example 6) or the aqueous sodium formate solution (Example 7) using the solid catalyst of the present invention. ..

(Example 8)
In a glass reaction container (inner diameter 9 mm, outer diameter 12 mm), a mesoporous organic silica powder having a bipyridone group coordinated to Ir obtained in Synthesis Example 2 as a solid catalyst Ir-BPyd-BPh-PMO (0.198 mmol-Ir). / G, 120 mg, 24 μmol-Ir) was charged and heated to 135 ° C. with a mantle heater. Then, the carrier gas (Ar) was circulated at a maximum flow rate of 5 ml / min. An aqueous methanol solution (methanol / water = 1/4 (molar ratio)) was placed in a syringe, the syringe was attached to a micro feeder, and the aqueous methanol solution was circulated at a flow rate of 1 ml / h, and the following reaction formula (E6):

The dehydrogenation gas phase reaction of the aqueous methanol solution represented by (3) was continued for 3 hours, and the generated gas was collected in a gas pack every 30 minutes. The components of the generated gas were measured by gas chromatography ("GC-8A" manufactured by Shimadzu Corporation, detector: TCD), the amount of hydrogen gas generated was calculated every 30 minutes, and the hydrogen generation rate was calculated. The result is shown in FIG.

As shown in FIG. 16, it was found that the hydrogen generation rate of 4 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (30 minutes). Further, the solid catalyst had a catalyst rotation speed of TON = 57 after 3 hours of reaction.

(Example 9)
Using mesoporous silica Ir-C3-BPyd-C3-FSM16 (0.228 mmol-Ir / g, 105 mg, 24 μmol-Ir) having a bipyridone group coordinated to Ir obtained in Synthesis Example 4 as a solid catalyst, dehydrogenation The following reaction formula (E7):

The dehydrogenation gas phase reaction of an aqueous methanol solution represented by The result is shown in FIG.

As shown in FIG. 17, it was found that the hydrogen generation rate of 4 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (60 minutes). Further, the solid catalyst had a catalyst rotation speed of TON = 112 after 6 hours of reaction.

(Comparative example 3)
In a 2-necked test tube equipped with a stirrer and a reflux tube under an argon atmosphere, Angew. Chem. Int. Ed. , 2015, 54 (31), pp 9057-9060, prepared by the iridium complex [IrCp ^* (bpyd) (OH)] Na (in the above formula, Cp ^* is tetramethylcyclopentadienyl coordination). Represents a child, and bpyd represents a 2,2′-bipyridonato ligand. 5.3 mg, 10 μmol) was weighed, and methanol (641 mg, 20 mmol) and water (1.44 g, 80 mmol) were further added. After attaching a reflux tube connected to a millimeter gas meter to the two-necked test tube, the two-necked test tube was immersed in an oil bath at 135 ° C., and the following reaction formula (C3):

The dehydrogenation liquid phase reaction of the aqueous methanol solution represented by (3) was continued for 3 hours, and the generated gas was collected in a gas pack every 30 minutes. The amount of generated gas was measured by a millimeter gas meter, and the components of the generated gas were measured by gas chromatography (“GC-8A” manufactured by Shimadzu Corporation, detector: TCD), and the reaction yield of hydrogen gas was measured. Was 0.24%. In addition, the amount of hydrogen gas generated was calculated every 30 minutes, and the hydrogen generation rate was calculated. The result is shown in FIG.

As shown in FIG. 18, the hydrogen production rate was 0.22 × 10 ⁻⁴ mol / h at the maximum, which was slower than that of the solid catalyst used in Example 8, and decreased with the passage of reaction time. I understood it. Furthermore, it was found that the homogeneous catalyst had a catalyst rotation speed of TON = 14 after 3 hours of reaction, and had a lower activity than the solid catalyst used in Example 8.

(Example 10)
Example 8 except that the filling amount of Ir-BPyd-BPh-PMO (0.198 mmol-Ir / g) was changed to 2.0 g (400 μmol-Ir) and the heating temperature by the mantle heater was changed to 180 ° C. Similarly, dehydrogenation gas phase reaction of an aqueous methanol solution was performed to calculate the hydrogen generation rate. The result is shown in FIG.

As shown in FIG. 19, it was confirmed that the hydrogen generation rate of 20 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (30 minutes). From the above results, it was found that even when the amount of the catalyst used was increased, the catalytic activity continued without being affected by CO ₂ produced as a by-product.

(Example 11)
A methanol aqueous solution was prepared in the same manner as in Example 10 except that the molar ratio of methanol to water in the aqueous methanol solution (methanol / water) was changed to 1/9, and the flow rate of the aqueous methanol solution was changed to 0.2 ml / h. A dehydrogenation gas phase reaction was performed and the yield of hydrogen gas was calculated. The result is shown in FIG.

As shown in FIG. 20, it was confirmed that the hydrogen generation reaction proceeded at a yield of 50% or more (based on methanol) at any reaction unit time (30 minutes). From the above results, it was found that the catalytic activity was sustained without being affected by CO ₂ produced as a by-product even under the condition of low flow rate in which the contact time between the aqueous methanol solution and the solid catalyst was long.

(Example 12)
Mesoporous organic silica powder Ir- (HO) BPy (having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst was placed in a two-necked Schlenk tube equipped with a stirrer and a reflux tube under an argon atmosphere. OH) -BPh-PMO (0.25 mmol-Ir / g, 8.0 mg, 2.0 μmol-Ir), dehydrated toluene (3 ml) and 1- (4-methoxyphenyl) ethanol (152.2 mg, 1 mmol) were weighed. did. The two-necked Schlenk tube was immersed in an oil bath at 130 ° C., heated and refluxed for 6 hours, and the following reaction formula (E8):

The dehydrogenation reaction of 1- (4-methoxyphenyl) ethanol represented by the formula (catalyst amount relative to secondary alcohol: 0.20 mol% -Ir) was carried out (this is newly used). After cooling, the Ir- (HO) BPy (OH) -BPh-PMO was collected by filtration using a membrane filter and washed with dehydrated toluene (15 ml). In addition, biphenyl was added to the obtained filtrate as an internal standard substance, and the amount of 4′-methoxyacetophenone produced by ¹ H-NMR or gas chromatography (“GC-4000 Plus” manufactured by GL-Sciences, detector: FID). Was measured to obtain the reaction yield, which was 99%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1- (4-methoxyphenyl) ethanol represented by the reaction formula (E8) in the same manner as in the case of the new use (this is the first reuse). Then, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of 4'-methoxyacetophenone produced is measured in the same manner as in the case of the new use to measure the reaction yield in the first reuse. I asked for the rate. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 99%, and the reaction yield in the second reuse was 99%.

(Example 13)
The following reaction formula (E9) was carried out in the same manner as in Example 12 except that 1- (2-methoxyphenyl) ethanol (152.2 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of 1- (2-methoxyphenyl) ethanol represented by the formula (catalyst amount relative to secondary alcohol: 0.20 mol% -Ir) was performed (this is a new use), and then the solid catalyst Ir was used. The-(HO) BPy (OH) -BPh-PMO was recovered. The amount of 2'-methoxyacetophenone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 87%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1- (2-methoxyphenyl) ethanol represented by the reaction formula (E9) in the same manner as in the case of the new use (this is referred to as the first reuse). After that, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of 2'-methoxyacetophenone produced is measured in the same manner as in the case of the new use to measure the reaction yield in the first reuse. I asked for the rate. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 81%, and the reaction yield in the second reuse was 74%.

(Example 14)
The following reaction formula (E10) was carried out in the same manner as in Example 12 except that 1- (4-tert-butylphenyl) ethanol (178.3 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of 1- (4-tert-butylphenyl) ethanol (catalyst amount relative to secondary alcohol: 0.20 mol% -Ir) represented by The catalyst Ir- (HO) BPy (OH) -BPh-PMO was recovered. Further, the production amount of 4'-tert-butylacetophenone was measured in the same manner as in Example 12, and the reaction yield was determined to be 98%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1- (4-tert-butylphenyl) ethanol represented by the reaction formula (E10) in the same manner as the above-mentioned new use (this is the first reuse). .. Then, in the same manner as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered, and the production amount of 4'-tert-butylacetophenone is measured to measure the amount in the first reuse. The reaction yield was determined. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 99%, and the reaction yield in the second reuse was 99%.

(Example 15)
The following reaction formula (E11) was carried out in the same manner as in Example 12 except that 1- (4-chlorophenyl) ethanol (156.6 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of 1- (4-chlorophenyl) ethanol represented by the following formula (catalyst amount relative to secondary alcohol: 0.20 mol% -Ir) was performed (this is newly used), and then the solid catalyst Ir- (HO) BPy (OH) -BPh-PMO was recovered. The amount of 4'-chloroacetophenone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 98%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Performed the dehydrogenation reaction of 1- (4-chlorophenyl) ethanol represented by the reaction formula (E11) in the same manner as in the case of the new use (this is the first reuse). Then, as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered, and the amount of 4'-chloroacetophenone produced is measured to measure the reaction yield in the first reuse. I asked for the rate. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 98%, and the reaction yield in the second reuse was 99%.

(Example 16)
The following reaction formula (E12) was carried out in the same manner as in Example 12 except that 1- (4-bromophenyl) ethanol (201.1 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of 1- (4-bromophenyl) ethanol (catalyst amount relative to secondary alcohol: 0.20 mol% -Ir) represented by The-(HO) BPy (OH) -BPh-PMO was recovered. The amount of 4'-bromoacetophenone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 98%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1- (4-bromophenyl) ethanol represented by the above reaction formula (E12) in the same manner as the above-mentioned new use (this is the first reuse). After that, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of 4'-bromoacetophenone produced is measured in the same manner as in the case of the new use to measure the reaction yield in the first reuse. I asked for the rate. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 98%, and the reaction yield in the second reuse was 98%.

(Example 17)
The following reaction formula (E13) was carried out in the same manner as in Example 12 except that 1- [4- (trifluoromethyl) phenyl] ethanol (190.2 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol. ):

After the dehydrogenation reaction of 1- [4- (trifluoromethyl) phenyl] ethanol represented by the formula (catalyst amount with respect to secondary alcohol: 0.20 mol% -Ir) was performed (this is newly used) The solid catalyst Ir- (HO) BPy (OH) -BPh-PMO was recovered. Further, the production amount of 4 '-(trifluoromethyl) acetophenone was measured in the same manner as in Example 12, and the reaction yield was determined to be 83%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Performed the dehydrogenation reaction of 1- [4- (trifluoromethyl) phenyl] ethanol represented by the above reaction formula (E13) in the same manner as in the case of the new use (this is referred to as the first reuse). To). After that, the Ir- (HO) BPy (OH) -BPh-PMO was recovered and the amount of 4 '-(trifluoromethyl) acetophenone produced was measured in the same manner as in the case of the new use, and the first re-use The reaction yield in use was determined. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 87%, and the reaction yield in the second reuse was 82%.

(Example 18)
1- (4-Cyanophenyl) ethanol (147.2 mg, 1 mmol) was used in place of 1- (4-methoxyphenyl) ethanol, and the Ir- (HO) BPy (OH) -BPh-PMO (0.25 mmol-) was used. The following reaction formula (E14) was carried out in the same manner as in Example 12 except that the amount of Ir / g) was changed to 20.0 mg (5.0 μmol-Ir).

The dehydrogenation reaction of 1- (4-cyanophenyl) ethanol represented by The-(HO) BPy (OH) -BPh-PMO was recovered. The amount of 4'-cyanoacetophenone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 84%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1- (4-cyanophenyl) ethanol represented by the reaction formula (E14) in the same manner as in the case of the new use (this is the first reuse). Then, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of 4'-cyanoacetophenone produced is measured in the same manner as in the case of the new use to measure the reaction yield in the first reuse. I asked for the rate. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 78%, and the reaction yield in the second reuse was 73%.

(Example 19)
The following reaction formula (E15) was carried out in the same manner as in Example 12 except that 1-phenyl-1-propanol (136.2 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of 1-phenyl-1-propanol represented by the following formula (catalyst amount to secondary alcohol: 0.20 mol% -Ir) was performed (this is newly used), and then the solid catalyst Ir- ( HO) BPy (OH) -BPh-PMO was recovered. The amount of propiophenone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 99%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 1-phenyl-1-propanol represented by the above reaction formula (E15) in the same manner as in the case of the new use (this is the first reuse). Then, in the same manner as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of propiophenone produced is measured to determine the reaction yield in the first reuse. I asked. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 97%, and the reaction yield in the second reuse was 98%.

(Example 20)
The following reaction formula (E16) was carried out in the same manner as in Example 12 except that 2-octanol (130.2 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

After the dehydrogenation reaction of 2-octanol (catalyst amount with respect to secondary alcohol: 0.20 mol% -Ir) represented by (using this as a new use), the solid catalyst Ir- (HO) BPy ( OH) -BPh-PMO was recovered. The amount of 2-octanone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 96%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Performed the dehydrogenation reaction of 2-octanol represented by the above reaction formula (E16) in the same manner as in the case of the above new use (this is the first reuse). Then, in the same manner as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered, and the production amount of 2-octanone is measured to determine the reaction yield in the first reuse. I asked. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 96%, and the reaction yield in the second reuse was 94%.

(Example 21)
6-Undecanol (172.3 mg, 1 mmol) was used in place of 1- (4-methoxyphenyl) ethanol, and the amount of Ir- (HO) BPy (OH) -BPh-PMO (0.25 mmol-Ir / g) was used. Was changed to 20.0 mg (5.0 μmol-Ir) and the heating reflux time was changed to 18 hours, and the following reaction formula (E17):

After the dehydrogenation reaction of 6-undecanol (catalyst amount relative to secondary alcohol: 0.50 mol% -Ir) represented by (using this as a new use), the solid catalyst Ir- (HO) BPy ( OH) -BPh-PMO was recovered. The amount of 6-undecanone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 99%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of 6-undecanol represented by the reaction formula (E17) in the same manner as in the case of the new use (this is the first reuse). Then, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of 6-undecanone produced is measured to determine the reaction yield in the first reuse as in the case of the new use. I asked. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 95%, and the reaction yield in the second reuse was 93%.

(Example 22)
The following reaction formula (E18) was carried out in the same manner as in Example 12 except that cyclohexanol (100.2 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

The dehydrogenation reaction of cyclohexanol (catalyst amount with respect to secondary alcohol: 0.20 mol% -Ir) represented by ) -BPh-PMO was recovered. The amount of cyclohexanone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 77%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of cyclohexanol represented by the above reaction formula (E18) in the same manner as in the case of the new use (this is the first reuse). After that, the Ir- (HO) BPy (OH) -BPh-PMO was recovered and the amount of cyclohexanone produced was measured to obtain the reaction yield in the first reuse, as in the case of the new use. .. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 79%, and the reaction yield in the second reuse was 71%.

(Example 23)
The following reaction formula (E19) was carried out in the same manner as in Example 12 except that cyclopentanol (86.1 mg, 1 mmol) was used instead of 1- (4-methoxyphenyl) ethanol.

After the dehydrogenation reaction of cyclopentanol (catalyst amount with respect to secondary alcohol: 0.20 mol% -Ir) represented by (using this newly), the solid catalyst Ir- (HO) BPy ( OH) -BPh-PMO was recovered. The amount of cyclopentanone produced was measured in the same manner as in Example 12, and the reaction yield was determined to be 95%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of cyclopentanol represented by the reaction formula (E19) in the same manner as in the case of the new use (this is the first reuse). Then, in the same manner as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of cyclopentanone produced is measured to determine the reaction yield in the first reuse. I asked. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 95%, and the reaction yield in the second reuse was 95%.

(Example 24)
Mesoporous organic silica powder Ir- (HO) BPy (having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst was placed in a two-necked Schlenk tube equipped with a stirrer and a reflux tube under an argon atmosphere. OH) -BPh-PMO (0.25 mmol-Ir / g, 10 mg, 2.5 μmol-Ir), dehydrated toluene (10 ml) and benzyl alcohol (54.07 mg, 0.5 mmol) were weighed. The two-necked Schlenk tube was immersed in an oil bath at 130 ° C., heated and refluxed for 18 hours, and the following reaction formula (E20):

The dehydrogenation reaction of benzyl alcohol (catalyst amount relative to primary alcohol: 0.50 mol% -Ir) represented by After cooling, the Ir- (HO) BPy (OH) -BPh-PMO was collected by filtration using a membrane filter and washed with dehydrated toluene (15 ml). In addition, biphenyl was added to the obtained filtrate as an internal standard substance, and the amount of benzaldehyde produced was measured by ¹ H-NMR or gas chromatography (“GC-4000 Plus” manufactured by GL-Sciences, detector: FID). The reaction yield was determined to be 98%.

  Next, a reuse experiment of the solid catalyst was conducted using the recovered Ir- (HO) BPy (OH) -BPh-PMO. That is, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1. Was subjected to the dehydrogenation reaction of benzyl alcohol represented by the above reaction formula (E20) in the same manner as in the above new use (this is the first reuse). Then, as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO was recovered and the amount of benzaldehyde produced was measured to obtain the reaction yield in the first reuse. .. In addition, a recycling experiment was conducted by repeating these series of operations, and the reaction yield in the second recycling was obtained. As a result, the reaction yield in the first reuse was 96%, and the reaction yield in the second reuse was 94%.

(Example 25)
The following reaction formula (E21) was carried out in the same manner as in Example 24 except that 4-methoxybenzyl alcohol (69.09 mg, 0.5 mmol) was used instead of benzyl alcohol.

After the dehydrogenation reaction of 4-methoxybenzyl alcohol (catalyst amount relative to the primary alcohol: 0.50 mol% -Ir) represented by (using this as a new use), the solid catalyst Ir- (HO) BPy (OH) -BPh-PMO was recovered. The amount of 4-methoxybenzaldehyde produced was measured in the same manner as in Example 24, and the reaction yield was determined to be 100%.

(Example 26)
The following reaction formula (E22) was carried out in the same manner as in Example 24 except that 4-bromobenzyl alcohol (93.52 mg, 0.5 mmol) was used instead of benzyl alcohol.

After the dehydrogenation reaction of 4-bromobenzyl alcohol (catalyst amount relative to primary alcohol: 0.50 mol% -Ir) represented by (using this as new use), solid catalyst Ir- (HO) BPy (OH) -BPh-PMO was recovered. The amount of 4-bromobenzaldehyde produced was measured in the same manner as in Example 24, and the reaction yield was determined to be 86%.

(Example 27)
The following reaction formula (E23) was carried out in the same manner as in Example 24 except that cyclohexanemethanol (57.10 mg, 0.5 mmol) was used instead of benzyl alcohol.

Of the cyclohexanemethanol represented by the following formula (catalyst amount relative to primary alcohol: 0.50 mol% -Ir) (this is newly used), and then solid catalyst Ir- (HO) BPy (OH ) -BPh-PMO was recovered. The amount of cyclohexanecarboxaldehyde produced was measured in the same manner as in Example 24, and the reaction yield was determined to be 50%.

  As shown in FIGS. 21 to 23, 1- (4-methoxyphenyl) ethanol (Example 12), 1- (2-methoxyphenyl) ethanol (Example 13), 1- (4-tert-butylphenyl) ) Ethanol (Example 14), 1- (4-chlorophenyl) ethanol (Example 15), 1- (4-bromophenyl) ethanol (Example 16), 1- [4- (trifluoromethyl) phenyl] ethanol (Example 17), 1- (4-cyanophenyl) ethanol (Example 18), 1-phenyl-1-propanol (Example 19), 2-octanol (Example 20), 6-undecanol (Example 21). ), Cyclohexanol (Example 22) and cyclopentanol (Example 23). By dehydrogenation with mesoporous organic silica powder having a bipyridine group, it was found that the corresponding ketones are obtained in high yield. It was also found that even when the solid catalyst was reused, the high yield in the dehydrogenation reaction of the secondary alcohol was maintained, and the solid catalyst can be repeatedly used.

  Further, as shown in FIG. 24, various kinds of benzyl alcohol (Example 24), 4-methoxybenzyl alcohol (Example 25), 4-bromobenzyl alcohol (Example 26), cyclohexanemethanol (Example 27) and the like. It was found that the primary alcohol can also be dehydrogenated using a mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir as a solid catalyst to obtain the corresponding aldehyde in a high yield. Further, it was found that even when the solid catalyst was reused, the high yield in the dehydrogenation reaction of the primary alcohol was maintained, and the solid catalyst can be repeatedly used.

(Example 28)
Mesoporous organic silica powder Ir- (HO) BPy (having a hydroxyl group-containing bipyridine group coordinated to Ir obtained in Synthesis Example 1 as a solid catalyst was placed in a two-necked Schlenk tube equipped with a stirrer and a reflux tube under an argon atmosphere. OH) -BPh-PMO (0.25 mmol-Ir / g, 10 mg, 2.5 μmol-Ir), dehydrated toluene (10 ml) and 2-octanol (65.1 mg, 0.5 mmol) were weighed. The two-necked Schlenk tube was immersed in an oil bath at 130 ° C., heated and refluxed for 6 hours, and the following reaction formula (E24):

The dehydrogenation reaction of 2-octanol represented by the formula (catalyst amount relative to secondary alcohol: 0.50 mol% -Ir) was performed (this is newly used). After cooling, the Ir- (HO) BPy (OH) -BPh-PMO was collected by filtration using a membrane filter and washed with dehydrated toluene (15 ml). In addition, biphenyl was added to the obtained filtrate as an internal standard substance, the amount of 2-octanone produced was measured by gas chromatography (“GC-4000 Plus” manufactured by GL-Sciences, detector: FID), and the reaction yield was measured. When the rate was calculated, it was 97%.

  Next, a reuse experiment of a solid catalyst was performed using the Ir- (HO) BPy (OH) -BPh-PMO recovered after the new use. That is, instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst. -In place of octanol, benzyl alcohol (54.07 mg, 0.5 mmol) was used, and the heating / refluxing time was changed to 18 hours, in the same manner as in the above new use, the following reaction formula (E25):

The dehydrogenation reaction of benzyl alcohol (catalyst amount relative to primary alcohol: 0.50 mol% -Ir) represented by the formula (1) was carried out (this is the first reuse). After that, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of benzaldehyde produced is measured to obtain the reaction yield in the first reuse, as in the case of the new use. As a result, it was 97%.

  Next, a reuse experiment of a solid catalyst was performed using the Ir- (HO) BPy (OH) -BPh-PMO recovered after the first reuse. That is, instead of the Ir- (HO) BPy (OH) -BPh-PMO obtained in Synthesis Example 1, the recovered Ir- (HO) BPy (OH) -BPh-PMO was used as a solid catalyst. The following reaction formula (E26):

The dehydrogenation reaction of 1-phenylethanol represented by the formula (catalyst amount relative to secondary alcohol: 0.50 mol% -Ir) was performed (this is the second reuse). Then, in the same manner as in the case of the new use, the Ir- (HO) BPy (OH) -BPh-PMO is recovered and the amount of acetophenone produced is measured to obtain the reaction yield in the second reuse. It was 95% when found.

  As shown in FIG. 25, by using a mesoporous organic silica powder having a hydroxyl group-containing bipyridine group coordinated to Ir as a solid catalyst, different kinds of alcohols can be used in new use, first reuse and second reuse. It was found that the corresponding ketones and aldehydes could be obtained in high yield even when the compound was dehydrogenated, and various carbonyl compounds could be obtained by changing the type of alcohol.

(Example 29)
Mesoporous organic silica powder Ir-C3-BPyd-C3-Et-PMO (0 having a bipyridone group coordinated to Ir obtained in Synthesis Example 7 as a solid catalyst was placed in a glass reaction container (inner diameter 9 mm, outer diameter 12 mm). .269 mmol-Ir / g, 89 mg, 24 μmol-Ir) was charged and heated to 100 ° C. with a mantle heater. Then, the carrier gas (Ar) was circulated at a maximum flow rate of 5 ml / min. An aqueous methanol solution (methanol / water = 1/9 (molar ratio)) was placed in a syringe, the syringe was attached to a micro feeder, and the aqueous methanol solution was circulated at a flow rate of 1 ml / h, and the following reaction formula (E27):

The dehydrogenation gas phase reaction of the aqueous methanol solution represented by the above was continued for 10 hours, and the generated gas was collected into the gas pack every hour. The components of the generated gas were measured by gas chromatography (“GC-8A” manufactured by Shimadzu Corporation, detector: TCD), the amount of hydrogen gas generated per hour was determined, and the hydrogen generation rate was calculated. The result is shown in FIG.

As shown in FIG. 26, after 2 hours from the start of the reaction, it was found that the hydrogen generation rate of 4.3 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (1 hour). It was The solid catalyst had a catalyst rotation number of TON = 181 after 10 hours of the reaction in the dehydrogenation gas phase reaction of the aqueous methanol solution.

(Example 30)
The following reaction formula (E28) was carried out in the same manner as in Example 29 except that an aqueous ethanol solution (ethanol / water = 1/9 (molar ratio)) was used instead of the aqueous methanol solution.

The dehydrogenation gas phase reaction of the aqueous ethanol solution represented by was performed to calculate the hydrogen generation rate. The result is shown in FIG.

As shown in FIG. 27, after 2 hours from the start of the reaction, it was found that the hydrogen generation rate of 1.6 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (1 hour). It was Further, the solid catalyst had a catalyst rotation number of TON = 64 after 10 hours of the reaction in the dehydrogenation gas phase reaction of the aqueous ethanol solution.

(Example 31)
The following reaction formula (E29) was carried out in the same manner as in Example 29 except that the heating temperature with the mantle heater was changed to 135 ° C. and 2-propanol was passed at a flow rate of 0.2 ml / h instead of the aqueous methanol solution.

The dehydrogenation gas phase reaction of 2-propanol represented by The result is shown in FIG.

As shown in FIG. 28, after 4 hours from the start of the reaction, it was found that the hydrogen generation rate of 12 × 10 ⁻⁴ mol / h or more was maintained at any reaction unit time (1 hour). Further, the solid catalyst had a catalyst rotation speed of TON = 347 after 10 hours of the reaction in the dehydrogenation gas phase reaction of 2-propanol.

  As described above, according to the present invention, it is possible to obtain a solid catalyst having excellent catalytic activity in the dehydrogenation reaction of alcohols, formic acid or formate salts. Therefore, the solid catalyst of the present invention is useful as a catalyst for producing a carbonyl compound from alcohols, a catalyst for producing hydrogen from alcohols, formic acid or a formate salt, and the like.

Claims (7)

Formula (1) below:
[In the formula (1), M represents a transition metal atom selected from the group consisting of iridium, rhodium and ruthenium, and L ¹ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclopentadienyl group. represents, L ² is the sulfoxide ligand, a nitrogen-containing aromatic ring ligand, amine ligand, a phosphine ligand, the ligand or a hydroxyl group is selected from the group consisting of ether ligands and aquo ligands Represents at least one group out of R ^{1 to} R ⁴ and at least one group out of R ^{5 to} R ⁸ is a hydroxyl group, and at least one group out of the remaining groups in R ^{1 to} R ⁴ and R ^At least one group of the remaining groups of ^{5 to} R ⁸ is represented by the following formula (2):
(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group and an imide group. An organic group or a single bond, R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, R ^b represents a hydrogen atom or a silyl group, k is 1 or 2, and i Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a combination of i and j is plural in each group represented by the formula (2). Independent, * is the binding site with the adjacent structure)
Which is a group represented by the following formula, wherein the remaining group of R ^{1 to} R ^{4 and} the remaining group of R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, It is a monovalent or divalent organic group selected from the group consisting of an alkoxy group, a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group and a cyano group, and R ⁴ and R ⁸ are They may combine with each other to form -CH = CH-]
A structure represented by, a transition metal-containing mesoporous organic silica having a coordination structure selected from the group consisting of its stereoisomers and tautomers,
A solid catalyst which is used for a dehydrogenation reaction of at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate salts.   The solid catalyst according to claim 1, wherein the structure represented by the formula (1) is contained in the skeleton of the transition metal-containing mesoporous organic silica. ^3. M in the formula (1) is iridium, L ¹ is a substituted or unsubstituted cyclopentadienyl group, and L ² is an aco ligand or a hydroxyl group. The solid catalyst according to. The solid catalyst according to any one of claims 1 to 3, wherein R ¹ and R ⁵ are hydroxyl groups, and R ² and R ⁶ are groups represented by the formula (2). ..   A method for producing a carbonyl compound, which comprises dehydrogenating alcohols using the solid catalyst according to any one of claims 1 to 4 to produce a carbonyl compound.   Using the solid catalyst according to any one of claims 1 to 4, at least one oxygen-containing compound selected from the group consisting of alcohols, formic acid and formate is dehydrogenated to generate hydrogen. A method for producing hydrogen, comprising:   The method for producing hydrogen according to claim 6, wherein dehydrogenation of the oxygen-containing compound is carried out in a gas phase.