Synthesis and X-ray characterization of [RhCl(C2H4)(PiPr3)]2. Multinuclear NMR and DFT investigation of its solid-state and solution reaction with dihydrogen. Ethene and propene hydrogenation by the solid Rh-hydrides

被引:9
作者
Angelini, Antonella [1 ,2 ]
Aresta, Michele [1 ,2 ]
Dibenedetto, Angela [1 ,2 ]
Pastore, Carlo [1 ,2 ]
Quaranta, Eugenio [1 ,2 ]
Chierotti, Michele R. [3 ]
Gobetto, Roberto [3 ]
Papai, Imre [4 ]
Graiff, Claudia [5 ]
Tiripicchio, Antonio [5 ]
机构
[1] Univ Bari, Dept Chem, I-70126 Bari, Italy
[2] CIRCC, I-70126 Bari, Italy
[3] Univ Turin, Dept Chem, I-10125 Turin, Italy
[4] Hungarian Acad Sci, Chem Res Ctr, H-1525 Budapest, Hungary
[5] Univ Parma, Dipartimento Chim Gen & Inorgan, I-43100 Parma, Italy
关键词
OXIDATIVE ADDITION-REACTIONS; RHODIUM COMPLEXES; CATALYTIC-HYDROGENATION; ALKYL DEHYDROGENATION; ETHYLENE; H-2; CHEMISTRY; CLUSTERS; LIGANDS; NUCLEAR;
D O I
10.1039/b903354h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
[RhCl(C2H4)(PiPr(3))](2) has been synthesised and structurally characterised. It shows an unusual planar Rh2Cl2 system, with the two phosphine and the two ethene molecules disposed trans to each other. It easily reacts with dihydrogen in solution and in the solid state to afford ethane and a dimeric complex of formula [RhCl(H)(2)P](2). The latter exhibits a high. uxionality both in solution and in the solid state making impossible the identification of a single limiting structure even at 183 K. 25 different hydride structures are possible, four of which have very low interconversion barriers (1-3 kcal mol(-1)) and cannot be blocked even at 183 K. A multinuclear NMR study and HECTOR experiments have allowed to identify the most probable structures that interconvert at 198 K. The solid hydrides are able to hydrogenate quite selectively ethene and propene at room temperature. A TON higher than 5600 and a TOF of 97 h(-1) was observed with ethene (for propene the values were 5200 and 79, respectively). Toluene was hydrogenated to methylcyclohexane at 323 K under an atmospheric pressure of H-2 with a TOF h(-1) equal to 15.
引用
收藏
页码:7924 / 7933
页数:10
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