Abstract
Phosphinidene complex Ph-P-W(CO)5 (2), generated from the appropriate phosphanorbornadiene complex 1, reacts with olefins to give the expected phosphiranes. The relative olefin reactivity toward 2 in toluene at 55 °C is tetramethylethylene (0.2), trimethylethylene (0.8), isobutylene (2-4), cis-2-butene (1.0), trans-2-butene (0.3), and 1-butene (0.2). The modest stereoselectivity of the phosphinidene addition reactions is reflected in the synlanti-phosphirane product ratios of several olefins and results form opposing steric and electronic influences. For cis-2-butene the synlanti ratio is 0.25 and the X-ray structure of the anit-isomer was determined. The surprising lack of olefin selectivity is compared with the olefin reactivities of various carbenes and particularly that of isopropylidene. The phosphinidene-olefin additions behave analogously to the carbene cyclopropanations and suggest the importance of entropie factors in the thermodynamically controlled reactions.
Original language | English |
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Pages (from-to) | 10966-10971 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 116 |
Issue number | 24 |
DOIs | |
Publication status | Published - 1 Nov 1994 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry