JP6538580B2 - Hydrogen oxidation catalyst - Google Patents
Hydrogen oxidation catalyst Download PDFInfo
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- JP6538580B2 JP6538580B2 JP2016019805A JP2016019805A JP6538580B2 JP 6538580 B2 JP6538580 B2 JP 6538580B2 JP 2016019805 A JP2016019805 A JP 2016019805A JP 2016019805 A JP2016019805 A JP 2016019805A JP 6538580 B2 JP6538580 B2 JP 6538580B2
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- hydrogen oxidation
- oxidation catalyst
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- 229910052739 hydrogen Inorganic materials 0.000 title claims description 38
- 239000001257 hydrogen Substances 0.000 title claims description 38
- 239000003054 catalyst Substances 0.000 title claims description 35
- 238000007254 oxidation reaction Methods 0.000 title claims description 29
- 230000003647 oxidation Effects 0.000 title claims description 28
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims 2
- 125000001033 ether group Chemical group 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012327 Ruthenium complex Substances 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000010718 Oxidation Activity Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 101100441092 Danio rerio crlf3 gene Proteins 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
本発明は、水素酸化触媒に関する。 The present invention relates to a hydrogen oxidation catalyst.
燃料電池の分野において、従来から、アノード触媒に着目し、燃料電池の性能の向上を図る試みがある。燃料電池のアノード触媒として広く利用されている白金触媒は、優れた水素酸化能を有するものの、その原料たる白金が高価かつ希少である。そのため、燃料電池用アノード触媒として、より安価な水素酸化触媒が求められている。
例えば、特許文献１には、硫黄及びリンを含有する二核遷移金属錯体（遷移金属はＦｅ又はＲｕ）の水素酸化触媒が開示されている。
In the field of fuel cells, there have been attempts to improve the performance of fuel cells, focusing on the anode catalyst. Although platinum catalysts widely used as anode catalysts for fuel cells have excellent hydrogen oxidizing ability, platinum as a raw material is expensive and scarce. Therefore, a less expensive hydrogen oxidation catalyst is required as an anode catalyst for fuel cells.
For example, Patent Document 1 discloses a hydrogen oxidation catalyst of a binuclear transition metal complex (transition metal is Fe or Ru) containing sulfur and phosphorus.
しかし、特許文献１に開示されているような水素酸化触媒は合成が困難という問題がある。
本発明は上記実情を鑑みて成し遂げられたものであり、本発明の目的は、比較的合成しやすく、且つ、水素酸化活性の高い水素酸化触媒を提供することである。
However, the hydrogen oxidation catalyst as disclosed in Patent Document 1 has a problem that synthesis is difficult.
The present invention has been accomplished in view of the above-mentioned circumstances, and an object of the present invention is to provide a hydrogen oxidation catalyst which is relatively easy to synthesize and has a high hydrogen oxidation activity.
本発明の水素酸化触媒は、エーテル側鎖を架橋硫黄上に有する硫黄架橋二核ルテニウム錯体を有し、
前記エーテル側鎖が、直鎖状もしくは分岐鎖状の飽和炭化水素鎖中のいずれかの炭素−炭素結合間にエーテル結合を１以上挿入しているものである、ことを特徴とする。
Hydrogen oxidation catalyst of the present invention, have a sulfur bridged dinuclear ruthenium complex having the ether side chains on the bridging sulfur,
The ether side chain is characterized in that one or more ether bonds are inserted between any carbon-carbon bond in a linear or branched saturated hydrocarbon chain .
本発明によれば、比較的合成しやすく、且つ、水素酸化活性の高い水素酸化触媒を提供することができる。 According to the present invention, it is possible to provide a hydrogen oxidation catalyst which is relatively easy to synthesize and has a high hydrogen oxidation activity.
本発明の水素酸化触媒は、エーテル側鎖を架橋硫黄上に有する硫黄架橋二核ルテニウム錯体を有することを特徴とする。 The hydrogen oxidation catalyst of the present invention is characterized by having a sulfur-bridged dinuclear ruthenium complex having an ether side chain on bridged sulfur.
本発明者らは、エーテル側鎖を架橋硫黄上に有する硫黄架橋二核ルテニウム錯体は、水素酸化反応速度が速いことを見出した。架橋硫黄上にエーテル側鎖を設けることで分子内にプロトン受容部位ができ、水素酸化活性が向上すると考えられる。 The present inventors have found that a sulfur-bridged dinuclear ruthenium complex having an ether side chain on bridged sulfur has a high rate of hydrogen oxidation reaction. By providing an ether side chain on the crosslinked sulfur, it is considered that a proton accepting site is formed in the molecule, and the hydrogen oxidation activity is improved.
本発明の水素酸化触媒は、エーテル側鎖を架橋硫黄上に有する硫黄架橋二核ルテニウム錯体を有するものであれば、特に限定されない。
本発明においてエーテル側鎖とは、直鎖状もしくは分岐鎖状の飽和炭化水素鎖中のいずれかの炭素−炭素結合間にエーテル結合を１以上挿入されているものをいう。また、エーテル側鎖に含まれるエーテル結合の数は１つであることが好ましい。例えば、直鎖状のエーテル側鎖は、（−Ｒ１−Ｏ−Ｒ２）で表すことができる。ここで、Ｒ１は、炭素数２〜４の二価の脂肪族炭化水素基であることが好ましく、具体的には、エチレン基、トリメチレン基、及びテトラメチレン基等が挙げられる。また、Ｒ２は、メチル基であることが好ましい。
また、本発明の水素酸化触媒の合成方法の具体例は、後述する実施例１〜３において詳述する。
The hydrogen oxidation catalyst of the present invention is not particularly limited as long as it has a sulfur-bridged dinuclear ruthenium complex having an ether side chain on bridged sulfur.
In the present invention, the ether side chain means one having one or more ether bonds inserted between any carbon-carbon bond in a linear or branched saturated hydrocarbon chain. Further, it is preferable that the number of ether bonds contained in the ether side chain is one. For example, a linear ether side chain can be represented by (-R 1 -O-R 2 ). Here, R 1 is preferably a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and specific examples thereof include an ethylene group, a trimethylene group, and a tetramethylene group. Further, R 2 is preferably a methyl group.
Moreover, the specific example of the synthesis | combining method of the hydrogen oxidation catalyst of this invention is explained in full detail in Examples 1-3 mentioned later.
本発明の水素酸化触媒は、水素酸化を必要とする全ての技術分野に広く応用可能である。
本発明の水素酸化触媒の用途の例としては、水素を燃料とする燃料電池のアノード触媒や、レドックスフロー電池のアノード触媒等が挙げられる。特に、大型化が進むレドックスフロー電池においては、本発明のように触媒効率が高く、かつ従来の白金触媒と比較して安価な水素酸化触媒は、コストを可能な限り低く抑える技術として有用である。
The hydrogen oxidation catalyst of the present invention is widely applicable to all technical fields requiring hydrogen oxidation.
Examples of uses of the hydrogen oxidation catalyst of the present invention include an anode catalyst of a fuel cell using hydrogen as a fuel, an anode catalyst of a redox flow cell, and the like. In particular, in a redox flow battery which is increasing in size, a hydrogen oxidation catalyst having high catalytic efficiency as in the present invention and being inexpensive as compared with a conventional platinum catalyst is useful as a technology for keeping the cost as low as possible. .
（実施例１）
［Ｃｐ＊ＲｕＣｌ］４（Ｃｐ＊＝η５−Ｃ５Ｍｅ５）（１６３ｍｇ）、及び、（ＭｅＯＣＨ２ＣＨ２Ｓ）２（５４ｍｇ）をテトラヒドロフラン（１０ｍＬ）中で２０時間攪拌した。
反応液を乾固し、残渣をジクロロメタン（１０ｍＬ）で抽出した。
抽出液にＡｇＯＴｆ（Ｔｆ＝ＳＯ２ＣＦ３）（７７ｍｇ）を加え、室温で１２時間攪拌した。
反応液を乾固したのち、残渣をエタノール−エーテルにより結晶化させることで、［Ｃｐ＊ＲｕＣｌ（μ２−Ｓ−ＣＨ２ＣＨ２ＯＭｅ）２ＲｕＣｐ＊（ＯＨ２）］ＯＴｆ（下記式（１）で示す水素酸化触媒１）を暗褐色結晶として得た（１７３ｍｇ、収率６８％）。
１Ｈ ＮＭＲ （ＣＤＣｌ３） δ３．８８（ｔ，Ｊ＝６Ｈｚ，４Ｈ），３．４６（ｓ，６Ｈ），３．２０（ｔ，Ｊ＝６Ｈｚ，４Ｈ），１．６８（ｓ，３０Ｈ）．Ａｎａｌ．Ｃａｌｃｄ ｆｏｒ Ｃ２７Ｈ４６ＣｌＦ３Ｏ６Ｒｕ２Ｓ３：Ｃ，３７．８２；Ｈ，５．４１％．Ｆｏｕｎｄ：Ｃ，３７．９５；Ｈ，５．１３％．
Example 1
[Cp * RuCl] 4 (Cp * = η 5 -C 5 Me 5) (163mg), and was stirred for 20 hours in (MeOCH 2 CH 2 S) 2 a (54 mg) in tetrahydrofuran (10 mL).
The reaction was evaporated to dryness and the residue was extracted with dichloromethane (10 mL).
AgOTf (Tf = SO 2 CF 3 ) (77 mg) was added to the extract and stirred at room temperature for 12 hours.
After the reaction solution is brought to dryness, the residue is crystallized with ethanol-ether to obtain [Cp * RuCl (μ 2 -S-CH 2 CH 2 OMe) 2 RuCp * (OH 2 )] OTf (the following formula (1 Hydrogen oxidation catalyst 1) shown in 2.) was obtained as dark brown crystals (173 mg, yield 68%).
1 H NMR (CDCl 3 ) δ 3.88 (t, J = 6 Hz, 4 H), 3.46 (s, 6 H), 3. 20 (t, J = 6 Hz, 4 H), 1.68 (s, 30 H) . Anal. Calcd for C 27 H 46 ClF 3 O 6 Ru 2 S 3: C, 37.82; H, 5.41%. Found: C, 37.95; H, 5.13%.
（実施例２）
［Ｃｐ＊ＲｕＣｌ］４（１６３ｍｇ）、及び、（ＭｅＯＣＨ２ＣＨ２ＣＨ２Ｓ）２（６４ｍｇ）をテトラヒドロフラン（１０ｍＬ）中で２０時間攪拌した。
反応液を乾固し、残渣をジクロロメタン（１０ｍＬ）で抽出した。
抽出液にＡｇＯＴｆ（８０ｍｇ）を加え室温で１２時間攪拌した。
反応液を乾固したのち、残渣をエタノール−エーテルにより結晶化させることで、［Ｃｐ＊ＲｕＣｌ（μ２−Ｓ−ＣＨ２ＣＨ２ＣＨ２ＯＭｅ）２ＲｕＣｐ＊（ＯＨ２）］ＯＴｆ（下記式（２）で示す、水素酸化触媒２）の暗褐色結晶を得た（１８７ｍｇ、収率７０％）。
１Ｈ ＮＭＲ （ＣＤＣｌ３）δ３．５８（ｔ，Ｊ＝６Ｈｚ，４Ｈ），３．３８（ｓ，６Ｈ），３．０２−２．９６（ｍ，４Ｈ），２．２３−２．１３（ｍ，４Ｈ），１．６７（ｓ，３０Ｈ）．Ａｎａｌ．Ｃａｌｃｄ ｆｏｒ Ｃ２９Ｈ５０ＣｌＦ３Ｏ６Ｒｕ２Ｓ３：Ｃ，３９．３４；Ｈ，５．６９％．Ｆｏｕｎｄ：Ｃ，３９．３６；Ｈ，５．４８％．
(Example 2)
[Cp * RuCl] 4 (163mg ), and was stirred for 20 hours in (MeOCH 2 CH 2 CH 2 S ) 2 a (64 mg) in tetrahydrofuran (10 mL).
The reaction was evaporated to dryness and the residue was extracted with dichloromethane (10 mL).
AgOTf (80 mg) was added to the extract and stirred at room temperature for 12 hours.
The reaction solution is brought to dryness, and the residue is crystallized with ethanol-ether to obtain [Cp * RuCl (μ 2 -S-CH 2 CH 2 CH 2 OMe) 2 RuCp * (OH 2 )] OTf (the following formula Dark brown crystals of the hydrogen oxidation catalyst 2) shown in (2) were obtained (187 mg, 70% yield).
1 H NMR (CDCl 3 ) δ 3.58 (t, J = 6 Hz, 4 H), 3.38 (s, 6 H), 3.02-2.96 (m, 4 H), 2.23-2.13 ( m, 4H), 1.67 (s, 30H). Anal. Calcd for C 29 H 50 ClF 3 O 6 Ru 2 S 3: C, 39.34; H, 5.69%. Found: C, 39.36; H, 5.48%.
（実施例３）
［Ｃｐ＊ＲｕＣｌ］４（５６ｍｇ）、及び、（ＭｅＯＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｓ）２（２４ｍｇ）をテトラヒドロフラン（５ｍＬ）中で２０時間攪拌した。
反応液を乾固し、残渣をジクロロメタン（５ｍＬ）で抽出した。
抽出液にＡｇＯＴｆ（２４ｍｇ）を加え室温で１２時間攪拌した。
反応液を乾固したのち、残渣をエタノールに溶解した。
溶液にエーテルを加えると暗褐色油状物が沈殿した。
沈殿を真空乾燥することで、［Ｃｐ＊ＲｕＣｌ（μ２−Ｓ−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＭｅ）２ＲｕＣｐ＊（ＯＨ２）］ＯＴｆ（下記式（３）で示す水素酸化触媒３）の褐色油状物を得た（５４ｍｇ、収率５９％）。
１Ｈ ＮＭＲ （ＣＤＣｌ３） δ３．４６（ｔ，Ｊ＝６Ｈｚ，４Ｈ），３．３６（ｓ，６Ｈ），２．９６（ｔ，Ｊ＝８Ｈ，４Ｈ），２．０８−１．９６（ｍ，４Ｈ），１．９０−１．７９（ｍ，４Ｈ），１．６７（ｓ，３０Ｈ）．
(Example 3)
[Cp * RuCl] 4 (56mg ), and was stirred for 20 hours in (MeOCH 2 CH 2 CH 2 CH 2 S) 2 a (24 mg) in tetrahydrofuran (5 mL).
The reaction was evaporated to dryness and the residue was extracted with dichloromethane (5 mL).
AgOTf (24 mg) was added to the extract and stirred at room temperature for 12 hours.
After drying the reaction solution, the residue was dissolved in ethanol.
A dark brown oil precipitated upon addition of ether to the solution.
By vacuum drying the precipitate, [Cp * RuCl (μ 2 -S-CH 2 CH 2 CH 2 CH 2 OMe) 2 RuCp * (OH 2 )] OTf (hydrogen oxidation catalyst 3 represented by the following formula (3)) A brown oil was obtained (54 mg, 59% yield).
1 H NMR (CDCl 3 ) δ 3.46 (t, J = 6 Hz, 4 H), 3.36 (s, 6 H), 2.96 (t, J = 8 H, 4 H), 2.08-1.96 ( m, 4H), 1.90-1.79 (m, 4H), 1.67 (s, 30H).
（比較例１）
［Ｃｐ＊ＲｕＣｌ］４（５４ｍｇ）、及び、（ＭｅＣＨ２ＣＨ２ＣＨ２Ｓ）２（１８ｍｇ）をテトラヒドロフラン（５ｍＬ）中で２０時間攪拌した。
反応液を乾固し、残渣をジクロロメタン（５ｍＬ）で抽出した。
抽出液にＡｇＯＴｆ（２６ｍｇ）を加え室温で１２時間攪拌した。
反応液を乾固したのち、残渣をジクロロメタン−ヘキサンにより結晶化させることで、［Ｃｐ＊ＲｕＣｌ（μ２−Ｓ−ＣＨ２ＣＨ２ＣＨ２Ｍｅ）２ＲｕＣｐ＊（ＯＨ２）］ＯＴｆ（下記式（４）で示す水素酸化触媒４）の暗褐色結晶を得た（４３ｍｇ、収率５１％）。
１Ｈ ＮＭＲ （ＣＤＣｌ３）δ２．９４（ｔ，Ｊ＝８Ｈｚ，４Ｈ），１．９３−１．８５（ｍ，４Ｈ），１．６７（ｓ，３０Ｈ），１．６３−１．５６（ｍ，４Ｈ），１．００（ｔ，Ｊ＝７Ｈｚ，６Ｈ）．Ａｎａｌ．Ｃａｌｃｄ ｆｏｒ Ｃ２９Ｈ５０ＣｌＦ３Ｏ４Ｒｕ２Ｓ３：Ｃ，４０．８１；Ｈ，５．９０％．Ｆｏｕｎｄ：Ｃ，４０．７０；Ｈ，５．６３％．
(Comparative example 1)
[Cp * RuCl] 4 (54mg ), and was stirred for 20 hours in (MeCH 2 CH 2 CH 2 S ) 2 a (18 mg) in tetrahydrofuran (5 mL).
The reaction was evaporated to dryness and the residue was extracted with dichloromethane (5 mL).
AgOTf (26 mg) was added to the extract and stirred at room temperature for 12 hours.
The reaction solution is brought to dryness, and the residue is crystallized from dichloromethane-hexane to give [Cp * RuCl (μ 2 -S-CH 2 CH 2 CH 2 Me) 2 RuCp * (OH 2 )] OTf (the following formula Dark brown crystals of the hydrogen oxidation catalyst 4 shown in (4) were obtained (43 mg, 51% yield).
1 H NMR (CDCl 3 ) δ 2.94 (t, J = 8 Hz, 4 H), 1.93-1.85 (m, 4 H), 1.67 (s, 30 H), 1.63-1.56 ( m, 4 H), 1.00 (t, J = 7 Hz, 6 H). Anal. Calcd for C 29 H 50 ClF 3 O 4 Ru 2 S 3: C, 40.81; H, 5.90%. Found: C, 40.70; H, 5.63%.
（比較例２）
非特許文献１に記載の方法に従い、［Ｃｐ＊ＲｕＣｌ（μ２−ＳＭｅ）２ＲｕＣｐ＊（ＯＨ２）］ＯＴｆ（下記水素酸化触媒５）を合成した。
(Comparative example 2)
According to the method described in Non-patent Document 1, [Cp * RuCl (μ 2 -SMe) 2 RuCp * (OH 2 )] OTf (the following hydrogen oxidation catalyst 5) was synthesized.
（比較例３）
非特許文献２に記載の方法に従い、［Ｃｐ＊ＲｕＣｌ（μ２−ＳＭｅ）２ＲｕＣｐ＊Ｃｌ］（下記水素酸化触媒６）を合成した。
(Comparative example 3)
According to the method described in Non-Patent Document 2, [Cp * RuCl (μ 2 -SMe) 2 RuCp * Cl] (the following hydrogen oxidation catalyst 6) was synthesized.
（比較例４）
非特許文献３に記載の方法に従い、［Ｃｐ＊Ｒｕ（μ２−ＳＭｅ）２ＲｕＣｐ＊（ＯＨ２）］（ＯＴｆ）２（下記水素酸化触媒７）を合成した。
(Comparative example 4)
According to the method described in Non-Patent Document 3, [Cp * Ru (μ 2 -SMe) 2 RuCp * (OH 2 )] (OTf) 2 (the following hydrogen oxidation catalyst 7) was synthesized.
［水素酸化活性の測定］
下記式（５）に示す反応を行った。具体的な手順は下記の通りである。
実施例１〜３、及び、比較例１〜４で得られた水素酸化触媒１〜７（下記式（５）中ｃａｔで表記）を２μｍｏｌ用意した。
そして、酸化剤［Ｃｐ２Ｆｅ］ＯＴｆ （Ｃｐ＝η５−Ｃ５Ｈ５）（０．４０ｍｍｏｌ）を入れたフラスコを７つ用意し、各フラスコに上記水素酸化触媒を１種類ずつ入れ、当該フラスコ内を１気圧の水素ガスで置換した。
その後、水（５ｍＬ）を加え室温で攪拌した。
酸化剤に由来する溶液の青色が消えたところで反応を終了した。反応時間ｔ（ｈ）の結果を表１に示す。
反応混合物にヘキサンを加え抽出を行った。
有機層を乾固した後、内部標準としてＣ６Ｍｅ６（１６ｍｇ）を加え１Ｈ ＮＭＲによりＣｐ２Ｆｅ（フェロセン）の収量を求めた。結果を表１に示す。
また、水層はジクロロメタンで洗浄した後に、フェノールフタレインを指示薬とする中和滴定を行い、ＨＯＴｆ収量を求めた。
反応時間ｔ、及び、Ｃｐ２Ｆｅ収量から、ＴＯＦ（ターンオーバー頻度）（１／ｈ）を算出した。結果を表１に示す。なお、ＴＯＦの算出式は以下の通りである。
ＴＯＦ＝Ｃｐ２Ｆｅ収量／（反応時間×触媒量×２）
[Measurement of hydrogen oxidation activity]
The reaction shown in the following formula (5) was performed. The specific procedure is as follows.
2 μmol of the hydrogen oxidation catalysts 1 to 7 (represented by cat in the following formula (5)) obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were prepared.
Then, seven flasks containing an oxidant [Cp 2 Fe] OTf (Cp = 5 5- C 5 H 5 ) (0.40 mmol) are prepared, and one kind of the above hydrogen oxidation catalyst is put in each flask, The inside of the flask was replaced with 1 atm of hydrogen gas.
After that, water (5 mL) was added and stirred at room temperature.
The reaction was terminated when the blue color of the solution derived from the oxidizing agent disappeared. The results of the reaction time t (h) are shown in Table 1.
The reaction mixture was extracted with hexane.
After drying the organic layer, C 6 Me 6 (16 mg) was added as an internal standard, and the yield of Cp 2 Fe (ferrocene) was determined by 1 H NMR. The results are shown in Table 1.
In addition, after washing the aqueous layer with dichloromethane, neutralization titration using phenolphthalein as an indicator was performed to determine the HOTf yield.
TOF (turnover frequency) (1 / h) was calculated from the reaction time t and the Cp 2 Fe yield. The results are shown in Table 1. The calculation formula of TOF is as follows.
TOF = Cp 2 Fe yield / (reaction time × catalyst amount × 2)
［水素酸化活性の評価結果］
表１に示すように、実施例１〜３と比較例１〜４では、実施例１〜３の方が、比較例１〜４よりも短い時間でＨＯＴｆ収量、Ｃｐ２Ｆｅ収量が増加するため、ＴＯＦが１０〜２７倍大きいことがわかる。
以上の結果より、実施例１〜３のような架橋硫黄上にエーテル側鎖を有する硫黄架橋ルテニウム錯体は、水素酸化活性が高いことがわかる。水素酸化活性向上の理由は、エーテル部位がプロトン受容部位として働いているか、又は、チオラート配位子の立体構造が反応性に影響を与えているためと推察される。
[Evaluation result of hydrogen oxidation activity]
As shown in Table 1, in Examples 1 to 3 and Comparative Examples 1 to 4, Examples 1 to 3 increase HOTf yield and Cp 2 Fe yield in a shorter time than Comparative Examples 1 to 4. , TOF is 10 to 27 times larger.
From the above results, it is understood that the sulfur-bridged ruthenium complex having an ether side chain on bridged sulfur as in Examples 1 to 3 has high hydrogen oxidation activity. The reason for the improvement of the hydrogen oxidation activity is presumed to be that the ether site acts as a proton accepting site or the steric structure of the thiolate ligand affects the reactivity.
Claims (1)
前記エーテル側鎖が、直鎖状もしくは分岐鎖状の飽和炭化水素鎖中のいずれかの炭素−炭素結合間にエーテル結合を１以上挿入しているものである、ことを特徴とする水素酸化触媒。 Have a sulfur bridged dinuclear ruthenium complex having the ether side chains on the bridging sulfur,
A hydrogen oxidation catalyst characterized in that the ether side chain has one or more ether bonds inserted between any carbon-carbon bonds in a linear or branched saturated hydrocarbon chain .
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