PNS-type ruthenium pincer complexes

Moti Gargir, Yehoshua Ben-David, Gregory Leitus, Yael Diskin-Posner, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The PNS pincer-type ligand 1 and the novel Ru(PNS) complexes 2-8 were synthesized and characterized. The (PNS)RuH(Cl)CO complex 2 was prepared by reaction of ligand 1 with RuH(Cl)CO(PPh 3) 3. 2 reacted with KHMDS (potassium bis(trimethylsilyl)amide) to form the symmetrical dimeric complex 4 via the intermediacy of the dearomatized complex (PNS*)Ru(H)CO 3, in which deprotonation of the benzylic-S "arm" took place. Reaction of 2 with excess NaH gave the dimeric 4, by a formal intermolecular attack of the benzylic "arm" on a second ruthenium center. Complex 4 underwent spontaneous transformation in solution to the dinuclear complex 5 via C-S bond cleavage, resulting in the loss of a S-bound tBu group. Treatment of 2 with KHMDS in the presence of PEt 3 resulted in the trapping of intermediate 3 in the form of the dearomatized complex 8. Reaction of 2 with LiHBEt 3 gave the trans-dihydride complex 6, which reacted with CO 2 to give the formato complex 7, in which the formato ligand is located trans to the hydride. Complexes 2, 4, and 5 were also investigated as catalysts for the dehydrogenative coupling of alcohols with amines.

Original languageEnglish
Pages (from-to)6207-6214
Number of pages8
JournalOrganometallics
Volume31
Issue number17
DOIs
Publication statusPublished - Sep 10 2012

Fingerprint

Ruthenium
Carbon Monoxide
ruthenium
ligands
Ligands
dihydrides
Deprotonation
amides
attack
hydrides
cleavage
potassium
amines
alcohols
trapping
Amides
Hydrides
Amines
catalysts
Potassium

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Gargir, M., Ben-David, Y., Leitus, G., Diskin-Posner, Y., Shimon, L. J. W., & Milstein, D. (2012). PNS-type ruthenium pincer complexes. Organometallics, 31(17), 6207-6214. https://doi.org/10.1021/om300516j

PNS-type ruthenium pincer complexes. / Gargir, Moti; Ben-David, Yehoshua; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Milstein, David.

In: Organometallics, Vol. 31, No. 17, 10.09.2012, p. 6207-6214.

Research output: Contribution to journalArticle

Gargir, M, Ben-David, Y, Leitus, G, Diskin-Posner, Y, Shimon, LJW & Milstein, D 2012, 'PNS-type ruthenium pincer complexes', Organometallics, vol. 31, no. 17, pp. 6207-6214. https://doi.org/10.1021/om300516j
Gargir M, Ben-David Y, Leitus G, Diskin-Posner Y, Shimon LJW, Milstein D. PNS-type ruthenium pincer complexes. Organometallics. 2012 Sep 10;31(17):6207-6214. https://doi.org/10.1021/om300516j
Gargir, Moti ; Ben-David, Yehoshua ; Leitus, Gregory ; Diskin-Posner, Yael ; Shimon, Linda J W ; Milstein, David. / PNS-type ruthenium pincer complexes. In: Organometallics. 2012 ; Vol. 31, No. 17. pp. 6207-6214.
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