Structural studies of lithiated enaminones: the 1-oxa-5-azapenta-dienyllithium fluxional heterocubane [(Pr-i;NCMeCHCMeOLi)(4)] and its dimeric hexamethylphosphoric triamide complex [{Pr-i;NCMeCHCMeOLi.OP(NMe2)(3)}(2)]

被引:18
作者
Brehon, M
Cope, EK
Mair, FS
Nolan, P
OBrien, JE
Pritchard, RG
Wilcock, DJ
机构
[1] UMIST,DEPT CHEM,MANCHESTER M60 1QD,LANCS,ENGLAND
[2] UNIV DUBLIN TRINITY COLL,DEPT CHEM,DUBLIN 2,IRELAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1997年 / 19期
关键词
D O I
10.1039/a704091a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Lithiation of 4-isopropylaminopent-3-en-2-one in hexane gave a 1-oxa-5-azapentadienyl compound [((PrCMeCHMeOLi)-C-i)(4)] 1, which comprises a tetrameric aggregate of Li-4 and O-4 interpenetrating tetrahedra in which chelating terminal nitrogens undergo a fluxional process around each face of the Li-4 tetrahedron in toluene solution. Addition of hexamethylphosphoric triamide (hmpa) produced a dimeric complex 2 in which oxygen bridges are retained. The crystal structures of both compounds were determined. Bond lengths indicate that an iminoenolate form of the ligand predominates, irrespective of aggregation state. The data are used to rationalise the selectivity of dimetallations of enaminones.
引用
收藏
页码:3421 / 3425
页数:5
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