2019 Fiscal Year Final Research Report
Development of new catalytic reactions over active sites on metal atoms of cluster complexes
| Project/Area Number |
15K18267
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Catalyst/Resource chemical process
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| Research Institution | Saitama University |
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Principal Investigator |
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| Project Period (FY) |
2016-04-01 – 2020-03-31
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| Keywords | 不均一系触媒 / クラスター錯体 / 無機材料 / 固体酸 |
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| Outline of Final Research Achievements |
When a silica gel-supported rhenium sulfide cluster whose external ligand are hydroxo ligand is treated in a hydrogen stream in the temperature range 250-500 °C, catalytic activity for the Friedel-Crafts acylation reaction of anisole and benzoyl chloride develops. The catalytically active site of the cluster is a hydroxo ligand is an uncoordinated metal site (Lewis acid site) developed by the loss of a water molecule from two hydroxo ligands.
The activation mechanism of the rhenium sulfide clusters is expected to differ depending on the external ligand. The rhenium sulfide clusters having phenoxide ligands were obtained by the direct substitution of terminal chloride ligands by reaction with silver p-cyanophenolate and p-nitrophenolate. The structure of the clusters exhibits a quasiperfect octahedral Re6 cluster geometry, as shown by the similar values of the interatomic Re-Re distances as well as by Re-Re-Re angles close to 60° and 90°.
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| Free Research Field |
触媒化学
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| Academic Significance and Societal Importance of the Research Achievements |
Friedel－Craftsアシル化は芳香族ケトンの工業的製造法として重要な反応の1つであるが、従来使用されている塩化アルミニウムを触媒として用いると化学両論量以上必要とする。クラスター錯体を触媒として用いることで不均一系での反応が可能となり、省エネルギー、低コスト化が期待できる。
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