Mononuclear and dinuclear complexes with a [Ru(tBu2PCH2CH2PtBu2)(CO)] core

Jose M Goicoechea, Mary F Mahon, Michael K Whittlesey, P G Anil Kumar, Paul S Pregosin

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28 Citations (Scopus)

Abstract

Thermolysis of solid [Ru(dtbpe)(CO)2Cl2] (2, dtbpe = tBu2PCH2CH2PtBu2) under vacuum affords the five-coordinate complex [Ru(dtbpe)(CO)Cl2] (4), which was shown by x-ray crystallog. to contain a weak remote agostic interaction. In soln., 4 can be readily trapped by CO, MeCN or H2O to give [Ru(dtbpe)(CO)(L)Cl2] (L = CO, 2; L = MeCN, 6; L = H2O, 7). Reaction of 4 with AgOTf/H2O yields the tris-aqua complex [Ru(dtbpe)(CO)(H2O)3](OTf)2 (8), which was structurally characterized and probed in soln. by pulsed-gradient spin echo (PGSE) NMR spectroscopy. The H2O ligands in 8 are labile and easily substituted to give [Ru(dtbpe)(CO)(NCCH3)3](OTf)2 (10) and [Ru(dtbpe)(CO)(DMSO)3](OTf)2 (11). In the presence of CO, the tris-aqua complex undergoes water-gas shift chem. with formation of the cationic hydride species [Ru(dtbpe)(CO)3H](OTf) (12) and CO2. X-ray crystal structures of complexes 2, 4, 6, 8 and 11-12 are reported along with those for [{Ru(dtbpe)(CO)}2(micro -Cl)2(micro -OTf)](OTf) (3), [{Ru(dtbpe)(CO)}2(micro -Cl)3][Ru(dtbpe)(CO)Cl3] (5) and [Ru(dtbpe)(CO)(H2O)2(OTf)](OTf) (9).
Original languageEnglish
Pages (from-to)588-597
Number of pages10
JournalDalton Transactions
Volume3
Publication statusPublished - 2005

Keywords

  • Water gas shift reaction (reaction of ruthenium bis(di-tert-butylphosphino)ethane carbonyl triaqua complex with CO)
  • ruthenium butylphosphinoethane carbonyl prepn structure
  • Molecular structure (of ruthenium bis(di-tert-butylphosphino)ethane carbonyl mononuclear and dinuclear complexes)
  • Crystal structure
  • diffusion const ruthenium butylphosphinoethane carbonyl complex
  • crystal structure ruthenium butylphosphinoethane carbonyl
  • water gas shift reaction ruthenium butylphosphinoethane carbonyl aqua

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