Ruthenium(II) porphyrin catalyzed imine aziridination and crystal structures of (meso-tetrakis(pentafluorophenyl)porphyrinato)ruthenium(II) complexes containing PhN=CH(p-ClPh), CPh2, and pyridine ligands

Yan Li, Philip Wai Hong Chan, Nian Yong Zhu, Chi Ming Che, Hoi Lun Kwong

Research output: Contribution to journalArticleResearchpeer-review

50 Citations (Scopus)

Abstract

A (meso-tetrakis(pentafluorophenyl)porphyrinato)ruthenium(II) complex of PhN=CH(p-ClPh) is prepared by reacting [Ru(F20-TPP)(CO)] (1) with a benzene solution of N-(p-chlorobenzylene)aniline. The crystal structure of {Ru(F20-TPP)(CO)[PhN=CH(p-ClPh)]} (10) shows the coordinated imine ligand in a cis configuration. Comparison with X-ray crystallographic data for [Ru(F20-TPP)(py)2] (11) revealed the axial Ru-N bond length of the imine complex (2.203 Å) to be slightly longer than that of the bis(pyridine) complex (2.108 Å). Spectral and structural data revealed the Ru-N(imine) bond to have single-bond character, and the Ru=C bond in [Ru(F20-TPP)(CPh2)] (7) has a bond distance of 1.842 Å, indicative of multiple-bond character. In the presence of diazo compounds, {Ru(F20-TPP)(CO)[PhN=CH-(p-ClPh)]} (10) and other related complexes mediated diastereoselective imine aziridination with product yields up to 86%. The mechanism is suggested to involve activation of the imine and diazo compounds by the ruthenium(II) porphyrin catalyst followed by nucleophilic addition of the imine to the diazo ester and subsequent cyclization to give the aziridine.

Original languageEnglish
Pages (from-to)54-66
Number of pages13
JournalOrganometallics
Volume23
Issue number1
DOIs
Publication statusPublished - 5 Jan 2004
Externally publishedYes

Cite this