104067-69-8Relevant articles and documents
Cycloaddition Reactions of Organometal Complexes, X. - Addition of Nitrenes to the Rh=C Bond of C5H5Rh(=C=CHR)P(iPr)3. Formation of Five-Membered Metalla-Heterocycles and a Ketenimine Rhodium Complex
Hoehn, Arthur,Werner, Helmut
, p. 881 - 886 (2007/10/02)
The complexes C5H5Rh(=C=CHR)P(iPr)3 (1, 3, 5) react with benzoyl azide almost quantitatively to produce the metalla-heterocycles (2, 4, 6).For 6 (R = Me), but not for 4 (R = Ph), the formation of E/Z isomers has been observed, the ratio of which is solvent-dependent.The protonation of 4 and 6-E/6-Z with CF3CO2H in presence of NH4PF6 lead via attack of the proton at the ring nitrogen atom to the PF6 salts of the cationic complexes 7 and 8 which also form E/Z isomers.On reaction of 3 with phenyl azide the Z isomer of the ketenimine complex C5H5Rh(C,N-ν2-PhN=C=ChPh)P(iPr)3 (9) is formed which in solution smoothly rearranges to give a 1:1 mixture of the Z and E isomers.
CYCLOADDITIONSREAKTIONEN VON ORGANOMETALLKOMPLEXEN VIII*. VINYLIDEN-METALLKOMPLEXE ALS BAUSTEINE FUER NEURATIGE FUENFGLIEDRIGE METALLA-HETEROCYCLEN
Werner, H.,Hoehn, A.,Weinand, R.
, p. C15 - C19 (2007/10/02)
Vinylidenemetal complexes such as C5H5Rh(=C=CHR)(PPr3i) (Ia,Ib) and C6H6Os(=C=CHPh)(PPr3i) (III) react with benzoylazide to form nearly quantitatively five-membered metalla heterocycles IIa, IIb and IV containing a MCNCO ring with an exocyclic C=C double bond.For M = Os, both Z- and E-isomers can be obtained.Protonation at the nitrogen atom of IIb leads to a cationic species for which also Z- and E-isomers can be observed.
