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Trifluoromethyl phosphaalkenes of the type F3CPC(OR)NR2: Synthesis, spectroscopic investigations, and ligand properties [1]

✍ Scribed by Joseph Grobe; Duc Le Van; Ulrike Althoff; Bernt Krebs; Mechtild Dartmann; Rolf Gleiter

Publisher: John Wiley and Sons
Year: 1991
Tongue: English
Weight: 745 KB
Volume: 2
Category: Article
ISSN: 1042-7163
DOI: 10.1002/hc.520020306

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✦ Synopsis

The one-pot reaction of the alcohol adducts F3CP(H)CF20R of perfluoro-2-phosphapropene with secondary amines in a 1 : 3 molar ratio affords the stable phosphaalkenes F3CP=C(OR)NR2 ( R = Me, Et) 1-4 in yields of 58%. NMR and He(Z) PE spectroscopic investigations show that the lone pair electrons on nitrogen and oxygen participate in n l r conjugation. In contrast to typical low-coordinated double bonds the new derivatives do not react with alcohols, amines, and 1,3-dienes. The derivatives are more closely related to the phosphaalkenes F3CP=C(F)NR2 than to perfluoro-2-phosphapropene. The reaction of F3CP=C(OEt)NMe2 (3) with Cr(C0)5THF yields the q'(P) complex Cr(C0)5[F3CP=C(OEt)NMe2] (7) with an unusually long sp2 PC bond ( I .809 A).

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## Abstract Reaction of the side‐on end‐on dinitrogen complex [{(NPN)Ta}~2~(μ‐H)~2~(μ‐η^1^:η^2^‐N~2~)] (1; in which NPN=(PhNSiMe~2~CH~2~)~2~PPh), with the Lewis acids XR~3~ results in the adducts [{(NPN)Ta}~2~(μ‐H)~2~(μ‐η^1^:η^2^‐NNXR~3~)], XR~3~=GaMe~3~ (2), AlMe~3~ (3), and B(C~6~F~5~)~3~ (4). Th