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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 language | English |
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Pages (from-to) | 1994-2003 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 138 |
Issue number | 6 |
Early online date | 4 Feb 2016 |
DOIs | |
Publication status | Published - 17 Feb 2016 |
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Dive into the research topics of 'Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs'. Together they form a unique fingerprint.Projects
- 1 Finished
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3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research