Functionalized Metalated Cavitands via Imidation and Late-Stage Elaboration
作者:Yanchuan Zhao、Timothy M. Swager
DOI:10.1002/ejoc.201500714
日期:2015.7
Efficient methods for the preparation of functionalized metallated cavitands are described. Functional groups can be either introduced by an imidation of metal-oxo complexes or by a late-stage elaboration of the imido ligands. By using diversified iminophosphorane (PPh3=NR) reagents, π-conjugated pyrene, redox active ferrocene and polymerizable norbornene moieties were successfully introduced. Furthermore
作者:Lars H. Peeck、Steffen Leuthäusser、Herbert Plenio
DOI:10.1021/om100628f
日期:2010.10.11
Grubbs-Hoveyda and Grubbs III type complexes with ferrocenyl- or NEt2-substituted NHC ligands were synthesized according to standard procedures. The electron donation of the NHC ligands in the respective ruthenium complexes can be modulated by oxidation of the ferrocenyl moiety or by protonation of the amino group. The neutral and the respective cationic (oxidized or protonated) ruthenium complexes were tested in the ROMP of norbornene. The change in the electron donation of NHC ligands upon protonation leads to a significant change in the double-bond geometry (from E/Z ratio = 0.78 to E/Z = 1.04) and in the microstructure of the resulting polynorbornene. Consequently, addition of acid and protonation of the living catalyst attached to the polymer chain during the polymerization reaction allows fine-tuning the E/Z ratio of the resulting polynorbornene.