Synthesis of ruthenium carbonyl complexes with phosphine or substituted Cp ligands, and their activity in the catalytic deoxygenation of 1,2-propanediol

Prasenjit Ghosh, Paul J. Fagan, William J. Marshall, Elisabeth Hauptmann, R. Morris Bullock

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Abstract

A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp iPr4)Ru(CO) 2H (Cp iPr4=C 5(i-C 3H 7) 4H) was prepared from the reaction of Ru 3(CO) 12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp iPr4)Ru(CO) 2H was determined by X-ray crystallography. The ruthenium hydride complex (C 5Bz 5)Ru(CO) 2H (Bz = CH 2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO) 2] 2, was produced from the reaction of 1,2,3trimethylindene with Ru 3(CO) 12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO) 2] 2(μ-H) -OTf -. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh) 3, PCy 3, PMe 3, P(P-C 6H 4F) 3] were prepared by reaction of Cp(CO) 2RuH with added L. Protonation of (Cp ipr4)Ru(CO) 2H, Cp ipr4Ru(CO) 2H, or Cp *Ru(CO)[P(OPh) 3]H by HOTf at -80 °C led to equilibria with the cationic dihydrogen complexes, but H 2 was released at higher temperatures. Protonation of CpRu[P(OPh) 3] 2H with HOTf gave an observable dihydrogen complex, (CpRu[P(OPh) 3] 22-H 2) +OTf - that was converted at -20 °C to the dihydride complex (CpRu[P(OPh) 3] 2(H)2} +OTf -. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out In sulfolane solvent with added HOTf under H 2 (750 psi) at 110 °C.

Original languageEnglish
Pages (from-to)6490-6500
Number of pages11
JournalInorganic Chemistry
Volume48
Issue number14
DOIs
Publication statusPublished - Jul 20 2009

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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