Pyridine-based sulfoxide pincer complexes of rhodium and iridium

Thomas Schaub, Udo Radius, Yael Diskin-Posner, Gregory Leitus, Linda J.W. Shimon, David Milstein

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)


The new pyridine-based sulfoxide pincer ligand 1 (2-(diethylaminomethyl)-6- (tert-butylsulfinylmethyl)pyridine = S(O)NN) reacts cleanly with Rh 2(COE)4Cl2 to form the neutral water- and air-stable Rh1 complex [Rh(S(O)NN)(NCCH3)], 1. The cationic complexes [Rh(S(O)NN(NCCH3)][BF4] (2) and [Ir(S(O)NN)(COE)][BF4] (5) were obtained by the reaction of 1 with the appropriate metal precursors. The corresponding carbonyl complexes [Rh(S(O)NN)(CO)][PF6] (4) and [Ir(S(O)NN)(CO)][BF4] (7) exhibit vCO in the IR spectra that shows that ligand 1 is a relatively poor a-donor ligand compared to the more common PNP-type ligands, resulting in rather electron-poor metal centers. The carbonyl compounds can be deprotonated to the remarkably stable dearomatized complexes Rh(S(O)NN*)(CO) (8) and Ir(S(O)NN*)(CO) (9). DFT studies on 8 revealed a high electron derealization over the pyridine ring system and the sulfur atom, which explains the high stability of 8 toward reprotonation. Complete protonation of 8 was achieved in acetic acid.

Original languageEnglish
Pages (from-to)1892-1901
Number of pages10
Issue number8
Publication statusPublished - Apr 28 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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