Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs

Owen J. Metters, Sebastian J K Forrest, Hazel A. Sparkes, Ian Manners, Duncan F. Wass*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

45 Citations (Scopus)

Abstract

We report intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene aryloxide and phosphine moieties that exhibit a broad range of small molecule activation chemistry that has previously been the preserve of only intramolecular pairs. Reactions with D2, CO2, THF, and PhCCH are reported. By contrast with previous intramolecular examples, these systems allow facile access to a variety of steric and electronic characteristics at the Lewis acidic and Lewis basic components, with the three-step syntheses of 10 new intermolecular transition metal FLPs being reported. Systematic variation to the phosphine Lewis base is used to unravel steric considerations, with the surprising conclusion that phosphines with relatively small Tolman steric parameters not only give highly reactive FLPs but are often seen to have the highest selectivity for the desired product. DOSY NMR spectroscopic studies on these systems reveal for the first time the nature of the Lewis acid/Lewis base interactions in transition metal FLPs of this type.

Original languageEnglish
Pages (from-to)1994-2003
Number of pages10
JournalJournal of the American Chemical Society
Volume138
Issue number6
Early online date4 Feb 2016
DOIs
Publication statusPublished - 17 Feb 2016

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