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 journalArticle

21 Citations (Scopus)

Abstract

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
JournalOrganometallics
Volume27
Issue number8
DOIs
Publication statusPublished - Apr 28 2008

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sulfoxide
Iridium
Rhodium
Carbon Monoxide
iridium
rhodium
pyridines
Ligands
ligands
Metals
Carbonyl compounds
carbonyl compounds
Electrons
Protonation
acetic acid
Sulfur
Discrete Fourier transforms
Acetic Acid
metals
electrons

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Schaub, T., Radius, U., Diskin-Posner, Y., Leitus, G., Shimon, L. J. W., & Milstein, D. (2008). Pyridine-based sulfoxide pincer complexes of rhodium and iridium. Organometallics, 27(8), 1892-1901. https://doi.org/10.1021/om701276s

Pyridine-based sulfoxide pincer complexes of rhodium and iridium. / Schaub, Thomas; Radius, Udo; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Milstein, David.

In: Organometallics, Vol. 27, No. 8, 28.04.2008, p. 1892-1901.

Research output: Contribution to journalArticle

Schaub, T, Radius, U, Diskin-Posner, Y, Leitus, G, Shimon, LJW & Milstein, D 2008, 'Pyridine-based sulfoxide pincer complexes of rhodium and iridium', Organometallics, vol. 27, no. 8, pp. 1892-1901. https://doi.org/10.1021/om701276s
Schaub T, Radius U, Diskin-Posner Y, Leitus G, Shimon LJW, Milstein D. Pyridine-based sulfoxide pincer complexes of rhodium and iridium. Organometallics. 2008 Apr 28;27(8):1892-1901. https://doi.org/10.1021/om701276s
Schaub, Thomas ; Radius, Udo ; Diskin-Posner, Yael ; Leitus, Gregory ; Shimon, Linda J W ; Milstein, David. / Pyridine-based sulfoxide pincer complexes of rhodium and iridium. In: Organometallics. 2008 ; Vol. 27, No. 8. pp. 1892-1901.
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