Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study

被引：6

作者：

Kozinets, Ekaterina M. ^{[1
,2
,3
]}

Fekete, Marianna ^{[4
]}

Filippov, Oleg A. ^{[3
]}

Belkova, Natalia V. ^{[3
]}

Shubina, Elena S. ^{[3
]}

Poli, Rinaldo ^{[1
,2
,5
]}

Duckett, Simon B. ^{[4
]}

Manoury, Eric ^{[1
,2
]}

机构：

[1] CNRS, LCC, F-31077 Toulouse 4, France

[2] Univ Toulouse, UPS, INPT, F-31077 Toulouse 4, France

[3] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia

[4] Univ York, Dept Chem, Ctr Hyperpolarisat Magnet Resonance, York YO10 5NY, N Yorkshire, England

[5] Inst Univ France, F-75005 Paris, France

来源：

DALTON TRANSACTIONS | 2013年 / 42卷 / 32期

基金：

英国工程与自然科学研究理事会; 俄罗斯基础研究基金会;

关键词：

HIGHLY ENANTIOSELECTIVE HYDROGENATION; RUTHENIUM DIHYDRIDE COMPLEXES; AB-INITIO PSEUDOPOTENTIALS; ASYMMETRIC HYDROGENATION; INDUCED POLARIZATION; H-2; ADDITION; IRIDIUM; THERMOCHEMISTRY; SPECTROSCOPY; CHEMISTRY;

D O I：

10.1039/c3dt51429c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of [RhCl(P,(SBu)-Bu-t)(COD)] (1) or [Rh(P,(SBu)-Bu-t)(COD)]BF4 (2) where (P,(SBu)-Bu-t) is CpFe[eta(5)-1,2-C5H3(PPh2)((CH2SBu)-Bu-t)] with H-2 in MeOH gives rise to COD hydrogenation and formation of a solvent-stabilized product. The formation of hydride species cannot be observed in view of a very rapid H/D exchange between H-2 and the solvent. Introduction of pyridine or acetonitrile slows down this exchange process and allows observation of diastereometric dihydride complexes, [Rh(P,(SBu)-Bu-t)(H)(2)(L)(2)](+), the stereo-chemistry of which was fully elucidated. The hydride site exchange rates have been derived from EXSY NMR experiments and used, with assistance from DFT calculation, to elucidate the isomerization and site exchange mechanisms.

引用

页码：11720 / 11730

页数：11

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