GENERATION AND REACTIVITY OF THE CHIRAL RHENIUM CHLOROBENZENE COMPLEX [ETA-5-C5H5)RE(NO)(PPH3)(CIC6H5)]+BF4- - AN IMPROVED FUNCTIONAL EQUIVALENT OF THE CHIRAL LEWIS ACID [(ETA-5-C5H5)RE(NO)(PPH3)]+BF4-

被引：63

作者：

KOWALCZYK, JJ

AGBOSSOU, SK

GLADYSZ, JA

机构：

[1] Department of Chemistry, University of Utah, Salt Lake City

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1990年 / 397卷 / 03期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

D O I：

10.1016/0022-328X(90)85333-T

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of (η5-C5H5)Re(NO)(PPh3)(CH3) (1) and HBF4 · OEt2 in C6H5Cl at -45°C gives the chlorobenzene complex [(η5-C5H5)Re(NO)(PPh3)(ClC6H5)]+BF-4 (5). The rhenium is bound chiefly to chlorine in 5, but other species, possibly η2-arene isomers, are apparent by 31P NMR. The relative amounts change upon warming, and new species appear. Complex 5 reacts with neutral donor ligands L (CH3CN, C6H5CH2CH=CH2, THF) to give the corresponding adducts [(η5-C5H5)Re(NO)(PPh3)(L)]+BF-4, halide ions X- to give halide complexes (η5-C5H5)Re(NO)(PPh3)(X), and HSi(OEt)3 to give hydride complex (η5-C5H5)Re(NO)(PPh3)(H) (74-91%). When 5 is generated from optically active 1, analogous reactions with L ((-)-(S)-2-phenylbutyronitrile, benzaldehyde) give adducts in high optical yields and with overall retention of configuration at rhenium. For example, carboxylate complex (+)-(RR)-(η5-C5H5)Re(NO)(PPh3)(O(C=O)-CH(OAc)C6H5) forms in > 99% d.e. upon treatment of 5 derived from (+)-(S)-1 with (-)-(R)-C6H5CH(OAc)COOH and then base. Thus, 5 serves as a functional equivalent of the chiral Lewis acid [(η5-C5H5)Re(NO)(PPh3)]+-superior in many aspects to the analogous dichloromethane complex reported earlier. © 1990.

引用

页码：333 / 346

页数：14

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