Insights into the Staudinger Reaction: Experimental and Theoretical Studies on the Stabilization of cis-Phosphazides

✍ Scribed by Christoph Widauer; Hansjörg Grützmacher; Igor Shevchenko; Volker Gramlich

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 503 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199910)1999:10<1659::aid-ejic1659>3.0.co;2-i

✦ Synopsis

The Staudinger-model reaction H 3 P (1) + HN 3 (2) Ǟ H 3 P=NH H 3 P=NH and N 2 . This decomposition can be effectively hampered by intramolecular donor-acceptor interactions as (5) + N 2 (6) has been investigated at the CCSD(T)/6-31G**// MP2(Full)/6-31G* level. Primary products formed in this shown by calculations on model compounds as well as by experiments. Thus the reaction of a methylene-σ 3 ,λ 3 -reaction are the phosphazides H 3 P=N-N=NH (3) which exist as trans and cis isomers. In contrast to some previous phosphanyl-σ 5 ,λ 5 -phosphorane with PhN 3 led to a new fourmembered heterocycle containing a thermally remarkable assumptions, cis-3 is 8.2 kcal mol -1 more stable than trans-3 but decomposes rather easily into the expected products stable cis-phosphazide moiety.

[a] Institute of Inorganic Chemistry, ETH-Zentrum, is 6.7 kcal mol Ϫ1 higher in energy than cis-3. Molecule 4