Journal of Inorganic and Organometallic Polymers and Materials

, Volume 24, Issue 1, pp 145–156

Platinum Phosphinito Catalysts for Nitrile Hydration

Authors

  • Spring Melody M. Knapp
    • Department of ChemistryUniversity of Oregon
  • Tobias J. Sherbow
    • Department of ChemistryUniversity of Oregon
  • Takiya J. Ahmed
    • Department of ChemistryUniversity of Oregon
  • Indre Thiel
    • Department of ChemistryUniversity of Oregon
  • Lev N. Zakharov
    • Department of ChemistryUniversity of Oregon
  • J. Jerrick Juliette
    • Dow Advanced Materials-Performance MonomersThe Dow Chemical Company
    • Department of ChemistryUniversity of Oregon
Article

DOI: 10.1007/s10904-013-9957-z

Cite this article as:
Knapp, S.M.M., Sherbow, T.J., Ahmed, T.J. et al. J Inorg Organomet Polym (2014) 24: 145. doi:10.1007/s10904-013-9957-z

Abstract

The reaction of PEt2OH with K2PtCl4 yields [PtCl{(PEt2O)2H}]2 (2). The X-ray crystal structure of 2 shows that the two chloride ligands bridge the two Pt atoms. The structure is unusual in that the PtCl2Pt unit is bent, which is the first example of a platinum phosphinito chloride-bridged dimer that is bent. Dimer 2 is a poor catalyst for the hydration of acetonitrile (and presumably other nitriles). Likewise, the monomeric catalyst that results from the reaction of 2 with sodium hydroxide is not a good hydration catalyst. In an attempt to form a more reactive monomeric catalyst, PtCl(PMe2OH){(PMe2O)2H} (1) was reacted with sodium hydroxide. This reaction resulted in the formation of two species, tentatively characterized as Na[PtCl(PMe2O){(PMe2O)2H}] (5) and Na[PtCl(OH){(PMe2O)2H}] (6). Complexes 5 and 6 could not be separated. However, the mixture of the two complexes quickly hydrated acetonitrile. The catalyst mixture of 5 and 6 was efficiently poisoned by cyanide, which prevented its use as a catalyst for the hydration of cyanohydrins.

Keywords

Nitrile hydration Platinum catalysts Phosphinito ligands Reaction mechanism 195Pt NMR spectroscopy

Supplementary material

10904_2013_9957_MOESM1_ESM.docx (95 kb)
Supplementary material 1 (DOCX 94 kb)

Copyright information

© Springer Science+Business Media New York 2013