膦胺铼配合物催化酮加氢制醇性能研究

doi:10.6023/cjoc202506024

摘要/Abstract

将金属中心配位有一个或两个双齿PN配体铼配合物(Ph₂PCH₂CH₂NH₂)Re(CO)₃Cl (1), (Ph₂PCH₂CH₂CH₂NH₂)- Re(CO)₃Cl (2)、(o-Ph₂PC₆H₄NH₂)Re(CO)₃Cl (3), [(Ph₂PCH₂CH₂NH₂)₂Re(CO)₂]Cl (4), [(Ph₂PCH₂CH₂CH₂NH₂)₂Re(CO)₂]Cl (5), 以及[(o-Ph₂PC₆H₄NH₂)₂Re(CO)₂]Cl (6)应用于均相催化酮类分子加氢制醇. 研究发现, 铼金属中心配位的PN配体数量对配合物加氢性能无显著影响. 围绕最优配合物2, 系统优化了催化剂用量、助剂和温度等反应参数. 在合适反应条件下, 2可以有效催化芳香酮、脂肪酮和杂环酮等近30余种酮类分子加氢制醇.

关键词: 铼配合物, 双齿PN配体, 催化加氢, 酮

Rhenium complexes (Ph₂PCH₂CH₂NH₂)Re(CO)₃Cl (1), (Ph₂PCH₂CH₂CH₂NH₂)Re(CO)₃Cl (2), (o-Ph₂PC₆H₄NH₂)- Re(CO)₃Cl (3), [(Ph₂PCH₂CH₂NH₂)₂Re(CO)₂]Cl (4), [(Ph₂PCH₂CH₂CH₂NH₂)₂Re(CO)₂]Cl (5), and [(o-Ph₂PC₆H₄NH₂)₂Re- (CO)₂]Cl (6), were applied for the first time in homogeneous catalytic hydrogenation of ketones to alcohols. Complexes with one PN ligand (1~3) and two PN ligands (4~6) exhibited comparable catalytic performance. Using optimal complex 2, the important factors with significant influences on the catalytic activity were well optimized, including the loading of catalyst, additive, temperature, and so on. Under suitable conditions, complex 2 effectively hydrogenated nearly 30 diverse ketones to their corresponding alcohols.

Key words: rhenium complex, bidentate PN ligand, catalytic hydrogenation, ketone

引用此文

方霄龙, 王俊, 徐舒婷, 李浩, 胡坤, 陈宜瑜, Yiyu. 膦胺铼配合物催化酮加氢制醇性能研究[J]. 有机化学, 2026, 46(1): 241-249.

Fang Xiaolong, Wang Jun, Xu Shuting, Li Hao, Hu Kun, Chen, Yiyu. Efficient Hydrogenation of Ketones to Alcohols Catalysed by Phosphinoamine Rhenium Complexes[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 241-249.

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图/表 7

图1. 代表性螯合型PNP配体配位的铼加氢催化剂

Figure 1. Representative rhenium catalysts bearing PNP-pincer ligand for hydrogenation reactions

图2. 铼配合物1~6的结构

Figure 2. Structures of rhenium complexes 1~6

图3. 铼配合物2 (a)、3 (b)和5 (c)的单晶结构图

Figure 3. X-ray crystal structures of rhenium complexes 2 (a), 3 (b) and 5 (c)

图4. 铼配合物1~6催化苯乙酮加氢制1-苯乙醇

Figure 4. Catalytic hydrogenation of acetophenone to 1-phenyl- ethanol by rhenium complexes 1~6 Reaction condition: 2.0 mmol of acetophenone (0.5 mmol/mL i-PrOH solution), 0.1 mol% Re complex, 10 mol% NaOEt, 2 MPa of H2, 100 ℃, 4 h

Entry	2/mol%	Temp./ ℃	p(H₂)/ MPa	Time/h	Yield^b/ %	TOF/ h^－1	TON
1	0.1	100	2	1	80	803	803
2	0.1	100	2	4	94	236	942
3	0.1	120	2	1	>99	999	999
4	0.1	100	1	4	90	226	904
5	0.1	80	2	8	64	80	636
6	0.1	80	1	8	62	78	624
7^c	0.1	100	2	4	10	26	104
8^d	0.1	100	2	4	52	130	518
9^e	0.1	100	2	4	81	203	812
10^f	0.01	100	5	12	>99	833	9990
11^g	0.002	120	5	12	50	2079	24950
12^h	0.001	120	5	12	42	3500	42000

表1. 铼(I)配合物2催化苯乙酮加氢制备1-苯乙醇a

Table 1. Catalytic hydrogenation of acetophenone to 1-phenyl- ethanol by 2

表2. 铼(I)配合物2催化酮类加氢制醇a

Table 2. Catalytic hydrogenation of ketones to alcohols by 2

图5. 2催化苯乙酮加氢制备1-苯乙醇可能的反应机理

Figure 5. Proposed reaction mechanism for the hydrogenation of acetophenone to 1-phenylethanol by 2

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