Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R = tBu, Ph) towards Electrophiles

✍ Scribed by Lothar Weber; Stefan Uthmann; Hans-Georg Stammler; Beate Neumann; Wolfgang W. Schoeller; Roland Boese; Dieter Bläser

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 540 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199912)1999:12<2369::aid-ejic2369>3.0.co;2-s

✦ Synopsis

The reaction of the carbonyl-functionalized phosphaalkenes [RC(OGaMe 3 )=P(GaMe 3 )C(NMe 2 ) 2 ] (10a,b). In contrast, one molecule of InMe 3 was bound to the phosphorus center of RC(O)P=C(NMe 2 ) 2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO) 4 ], [Fe 2 (CO) 9 ] or [{(Z)-cyclooctene}Cr(CO) 5 ] also phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO) n }C(NMe 2 ) 2 ] (R = tBu, Ph; M = Ni, Me 3 SiOSO 2 CF 3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe 3 )= n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations

reported here underline the versatile chemistry of PC(NMe 2 ) 2 ]SO 3 CF 3 (5a,b). Similarly, the Lewis acids B(C 6 F 5 ) 3 , Al(tBu) 2 Cl and AlMe 3 were ligated to the oxygen phosphaalkenes and emphasize a relationship between carbonyl-functionalized phosphaalkenes and the well-atom of the carbonyl group. Two equivalents of GaMe 3 were added to the oxygen and phosphorus atom of the investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported. phosphaalkene to yield the thermolabile complexes [a] Fakultät für Chemie der Universität Bielefeld, inverse electron distribution of the PϭC π-bond. [3] In order