Synthesis, reactivity and X-ray crystal structure of an uncomplexed 1-phosphabarrelene: application to the synthesis of 1,1 '-bis(dimethylsilylphosphinine)ferrocenes

Citation
S. Welfele et al., Synthesis, reactivity and X-ray crystal structure of an uncomplexed 1-phosphabarrelene: application to the synthesis of 1,1 '-bis(dimethylsilylphosphinine)ferrocenes, NEW J CHEM, 25(10), 2001, pp. 1264-1268
Citations number
32
Categorie Soggetti
Chemistry
Journal title
NEW JOURNAL OF CHEMISTRY
ISSN journal
11440546 → ACNP
Volume
25
Issue
10
Year of publication
2001
Pages
1264 - 1268
Database
ISI
SICI code
1144-0546(200110)25:10<1264:SRAXCS>2.0.ZU;2-V
Abstract
The 5,6-diphenyl-3-tertiobutyl-1,2-azaphosphinine 3 reacts with bis(phenyle thynyldimethylsilyl)ferrocene, 2, to afford a mixture of the phosphinine 4, resulting from the cycloaddition of 3 with one alkynyl group of 2, and 1-p hosphabarrelene, 5, whose formation results from an intramolecular [4 + 2] cycloaddition between the remaining alkynyl group of the ferrocenyl ligand and the 1,4-phosphabutadienic system of 4. The X-ray structure of compound 5 was obtained and shows no particular strain in the molecule. Competitive experiments have shown that, at high temperature, phosphinine 4 equilibrate s with barrelene 5. Synthesis of a bidentate ligand 6, incorporating two di methylsilyl-substituted phosphinines, was achieved by reacting the azaphosp hinine 3 with half an equivalent of the ferrocene derivative 2. The mixed l igand 8, incorporating two different phosphinine subunits, was also prepare d using a two-step sequence by reacting a mixture of 4 and 5 with diazaphos phinine 1. This reaction first produced an intermediate azaphosphinine-phos phinine ligand 7, which was then trapped with trimethylsilylacetylene to af ford ligand 8.