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Ruthenium complexes featuring cooperative phosphine–pyridine–iminophosphorane (PNN) ligands: synthesis, reactivity and catalytic activity†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-09-17 00:00:00 , DOI: 10.1039/c8dt03488e
Thibault Cheisson 1, 2, 3, 4, 5 , Louis Mazaud 1, 2, 3, 4, 5 , Audrey Auffrant 1, 2, 3, 4, 5
Affiliation  

The coordination to ruthenium(II) centres of two phosphine–pyridine–iminophosphorane ligands LR (PPh2CH2(C6H3N)CH2N[double bond, length as m-dash]PR3, R = Ph or Cy) differing by the nature of the substituent of the P[double bond, length as m-dash]N phosphorus was explored. Coordination to [RuCl2(PPh3)3] afforded the complexes [RuLRCl2(PPh3)] that were successfully deprotonated at the acidic phosphinomethyl position. With LCy, coordination led to a mixture of two isomers. The complexes [RuLRHCl(PPh3)] were similarly obtained from [RuHCl(PPh3)3]. The stability of these complexes depends on the ligand substitution pattern; with LPh a CH activation process took place, while [RuLCyHCl(PPh3)] was thermally stable. Deprotonation of this latter complex was achieved and gave a catalytically competent species for the acceptorless dehydrogenative coupling of alcohols.

中文翻译:

具有协同膦-吡啶-亚氨基正膦(PNN)配体的钌配合物:合成,反应性和催化活性

两个膦-吡啶-亚氨基正膦配体L R(PPh 2 CH 2(C 6 H 3 N)CH 2 N PR 3,R = Ph或Cy)与钌(II)中心的配位因取代基的性质不同而不同探索了P N磷。与[RuCl 2(PPh 33 ]配位得到[Ru L R Cl 2(PPh 3)]配合物,其在酸性膦基甲基位置成功地去质子化。与L Cy[双键,长度为m-破折号][双键,长度为m-破折号],配位导致两种异构体的混合。类似地从[RuHCl(PPh 33 ]获得配合物[Ru L R HCl(PPh 3)]。这些配合物的稳定性取决于配体的取代方式。用L Ph进行CH活化过程,而[Ru L Cy HCl(PPh 3)]是热稳定的。实现了后一种配合物的去质子化,并给出了用于醇的无受体脱氢偶联的催化活性物质。
更新日期:2018-09-17
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