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Reactivity of Sterically Unencumbered Transient Nitrilium Phosphanylide Complexes Towards 1‐Piperidinocarbonitrile: A Case Study
Author(s) -
Streubel Rainer,
Schiemann Udo,
Huy Ngoc Hoa Tran,
Mathey François
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200112)2001:12<3175::aid-ejic3175>3.0.co;2-c
Subject(s) - chemistry , steric effects , reactivity (psychology) , transient (computer programming) , combinatorial chemistry , stereochemistry , medicine , alternative medicine , pathology , computer science , operating system
The thermal decomposition of the 7‐phosphanorbornadiene complexes 6a , b in xylene at 120 °C in the presence of two equivalents of 1‐piperidinocarbonitrile yielded the 2 H ‐1,3,2‐azaphosphole complexes 11a , b and the 2 H ‐1,4,2‐azaphosphole complexes 12a − c in ratios of 7:4 ( 11a : 12a ) and 1:5 ( 11b : 12b ). Remarkably, the two atropisomers 12b and 12c were obtained (ratio: 5:1) in the case of the P ‐phenyl‐substituted 2 H ‐1,4,2‐azaphosphole complex. Interestingly, the product ratios of both reactions were approximately the same if neat 1‐piperidinocarbonitrile was used as the solvent. The reaction of complexes 6a,b with Cu I Cl and 1‐piperidinocarbonitrile, with exclusion of light, also furnished the 2 H ‐1,3,2‐azaphosphole complexes 11a,b as the main products. In the case of complex 6a , a by‐product was detected by 31 P NMR spectroscopy but could not be isolated. Complexes 11a,b , 12a and 13 were purified by column chromatography at low temperature and characterized by NMR and MS spectroscopic means and elemental analysis, whereas only a 1:1 mixture of 12b and 12c could be characterized.