Quan Yangjian, Lan Guangxu, Shi Wenjie, Xu Ziwan, Fan Yingjie, You Eric, Jiang Xiaomin, Wang Cheng, Lin Wenbin
Department of Chemistry, The University of Chicago, Chicago, IL, 60637, USA.
College of Chemistry and Chemical Engineering, iCHEM, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2021 Feb 8;60(6):3115-3120. doi: 10.1002/anie.202011519. Epub 2020 Dec 3.
We report the design of a bifunctional metal-organic layer (MOL), Hf -Ru-Co, composed of [Ru(DBB)(bpy) ] [DBB-Ru, DBB=4,4'-di(4-benzoato)-2,2'-bipyridine; bpy=2,2'-bipyridine] connecting ligand as a photosensitizer and Co(dmgH) (PPA)Cl (PPA-Co, dmgH=dimethylglyoxime; PPA=4-pyridinepropionic acid) on the Hf secondary building unit (SBU) as a hydrogen-transfer catalyst. Hf -Ru-Co efficiently catalyzed acceptorless dehydrogenation of indolines and tetrahydroquinolines to afford indoles and quinolones. We extended this strategy to prepare Hf -Ru-Co-OTf MOL with a [Ru(DBB)(bpy) ] photosensitizer and Hf SBU capped with triflate as strong Lewis acids and PPA-Co as a hydrogen transfer catalyst. With three synergistic active sites, Hf -Ru-Co-OTf competently catalyzed dehydrogenative tandem transformations of indolines with alkenes or aldehydes to afford 3-alkylindoles and bisindolylmethanes with turnover numbers of up to 500 and 460, respectively, illustrating the potential use of MOLs in constructing novel multifunctional heterogeneous catalysts.
我们报道了一种双功能金属有机层（MOL），即Hf -Ru-Co的设计，它由作为光敏剂的连接配体[Ru(DBB)(bpy) ] [DBB-Ru，DBB = 4,4'-二(4-苯甲酸根)-2,2'-联吡啶；bpy = 2,2'-联吡啶]和作为氢转移催化剂的位于Hf二级结构单元（SBU）上的Co(dmgH) (PPA)Cl（PPA-Co，dmgH = 二甲基乙二肟；PPA = 4-吡啶丙酸）组成。Hf -Ru-Co能高效催化二氢吲哚和四氢喹啉的无受体脱氢反应，生成吲哚和喹诺酮。我们扩展了这一策略，制备了Hf -Ru-Co-OTf MOL，它具有[Ru(DBB)(bpy) ]光敏剂、以三氟甲磺酸盐作为强路易斯酸封端的Hf SBU以及作为氢转移催化剂的PPA-Co。凭借三个协同活性位点，Hf -Ru-Co-OTf能够有效地催化二氢吲哚与烯烃或醛的脱氢串联转化反应，分别生成3-烷基吲哚和双吲哚甲烷，其转换数高达500和460，这说明了金属有机层在构建新型多功能多相催化剂方面的潜在用途。
