Mixed metal II-metal IV hybrid fluorides

Jérôme Lhoste, Karim Adil, Armel Le Bail, Marc Leblanc, Annie Hémon-Ribaud, Vincent Maisonneuve*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Six M II-M IV type II hybrid fluorides (M II = Cu, Ni; M IV = Si, Ti, Mo) are compared: (Ni(en) 3) ·(TiF 6), [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo), [H 3O] 2·(SiF 6(CuF(py) 4) 2) ·(F) 2 and Cu(en) 2MF 6 (M IV = Ti, Si). They are obtained at 160 °C under microwave heating and the structures are determined either from single crystal or powder X-ray diffraction data. All phases involve neutral amines that are linked to M II cations, a feature of type II hybrids. In (Ni(en) 3)·(TiF 6), the cationic (Ni(en) 3) 2+ and anionic (TiF 6) 2- entities are isolated. In [Hpy] 2·(Cu(py) 4(TiF 6) 2) and [Hpy] 2·(Cu(py) 4(MoF 6) 2), extra non metal bonded amines are protonated to give [Hpy] + cations that exchange hydrogen bonds with fluoride anions, a feature of type I hybrids. All phases exhibit a fully fluorinated octahedral environment of M IV cations, at the opposite from previously reported [H 3O] 2·(NbOF 5(CuF(py) 4) 2) ·(F) 2 or [Hpy] 2·(Cu(py) 4) (MoO 2F 4) 2. In [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo) or [H 3O] 2·(SiF 6(CuF(py) 4) 2)·(F) 2, Cu II and M IV entities are associated by fluoride anions to give anionic or neutral trimetallic clusters, respectively; the results of thermal analysis suggest that the oxidation state is +IV for molybdenum and it is proposed that H 3O + and "free" F - ion pairs can be replaced locally by H 2O and HF couples. In Cu(en) 2MF 6, the Cu II and M IV entities alternate and build infinite chains

Original languageEnglish (US)
Pages (from-to)29-34
Number of pages6
JournalJournal of Fluorine Chemistry
Volume134
DOIs
StatePublished - Feb 1 2012

Keywords

  • Hybrid fluorides
  • Hydrothermal synthesis
  • Microwave heating

ASJC Scopus subject areas

  • Biochemistry
  • Environmental Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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