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Synthesis and Characterization of RhIII–MII (M = Pt, Pd) Heterobimetallic Complexes Based on a Bisphosphine Ligand: Tandem Reactions Using Ethanol
Organometallics ( IF 2.5 ) Pub Date : 2020-10-27 , DOI: 10.1021/acs.organomet.0c00594 Zeinab Mandegani 1 , Asma Nahaei 1 , Mahshid Nikravesh 2 , S. Masoud Nabavizadeh 1 , Hamid R. Shahsavari 2 , Mahdi M. Abu-Omar 3
Organometallics ( IF 2.5 ) Pub Date : 2020-10-27 , DOI: 10.1021/acs.organomet.0c00594 Zeinab Mandegani 1 , Asma Nahaei 1 , Mahshid Nikravesh 2 , S. Masoud Nabavizadeh 1 , Hamid R. Shahsavari 2 , Mahdi M. Abu-Omar 3
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1,1-Bis(diphenylphosphino)methane (dppm) was used as a linker ligand for the preparation of a series of heterobimetallic RhIII–PtII and RhIII–PdII complexes. These complexes were characterized by means of several analytical and spectroscopic methods. The catalytic activities of these heterobimetallic complexes were carried out in three different tandem reactions: namely, transfer hydrogenation (TH)/dehalogenation (DH), TH/Suzuki–Miyaura coupling, and coupling of benzylic alcohols with nitrobenzenes for Schiff base construction. Ethanol was used as both the solvent and an inexpensive TH reagent, where a broad substrate scope was demonstrated for these tandem reactions. All reactions proceeded smoothly in air at 80–90 °C. The RhIII–PdII complex showed superior catalytic performance in comparison to the RhIII–PtII complexes, its monometallic counterparts, and mixtures of monometallic (RhIII + PdII) complexes. The result demonstrates a cooperative effect between the Rh and Pd metal centers. A mechanism for the catalytic tandem reactions was investigated. It was found that alcohol medium and base are essential.
中文翻译：
基于双膦配体的Rh III -M II（M = Pt，Pd）杂双金属配合物的合成和表征：使用乙醇的串联反应
1,1-双（二苯基膦基）甲烷（dppm）被用作连接体配体，用于制备一系列异双金属Rh III -Pt II和Rh III -Pd II配合物。这些配合物通过几种分析和光谱学方法表征。这些异双金属配合物的催化活性在三个不同的串联反应中进行：即转移氢化（TH）/脱卤化（DH），TH / Suzuki-Miyaura偶联以及苄醇与硝基苯的偶联以形成Schiff碱。乙醇既用作溶剂，又用作廉价的TH试剂，在这些串联反应中，底物范围广。所有反应均在80–90°C的空气中顺利进行。RhIII -Pd II复合物显示相比于铑优良的催化性能III -Pt II复合物，其单金属对应物，和单金属的混合物（铑III +钯II）配合物。结果证明了Rh和Pd金属中心之间的协同作用。研究了催化串联反应的机理。发现酒精介质和碱是必不可少的。
更新日期：2020-11-09
中文翻译：
基于双膦配体的Rh III -M II（M = Pt，Pd）杂双金属配合物的合成和表征：使用乙醇的串联反应
1,1-双（二苯基膦基）甲烷（dppm）被用作连接体配体，用于制备一系列异双金属Rh III -Pt II和Rh III -Pd II配合物。这些配合物通过几种分析和光谱学方法表征。这些异双金属配合物的催化活性在三个不同的串联反应中进行：即转移氢化（TH）/脱卤化（DH），TH / Suzuki-Miyaura偶联以及苄醇与硝基苯的偶联以形成Schiff碱。乙醇既用作溶剂，又用作廉价的TH试剂，在这些串联反应中，底物范围广。所有反应均在80–90°C的空气中顺利进行。RhIII -Pd II复合物显示相比于铑优良的催化性能III -Pt II复合物，其单金属对应物，和单金属的混合物（铑III +钯II）配合物。结果证明了Rh和Pd金属中心之间的协同作用。研究了催化串联反应的机理。发现酒精介质和碱是必不可少的。
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