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

Journal of the American Chemical Society
Owen J MettersDuncan F Wass

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.

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Citations

Mar 24, 2016·Journal of the American Chemical Society·Nikola S LambicElon A Ison
Jun 1, 2017·Inorganic Chemistry·Diane A DickieRichard A Kemp
Mar 18, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kejian Chang, Xin Xu
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Sep 27, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Nikolaos TsoureasF Geoffrey N Cloke
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Oct 8, 2019·Chemical Communications : Chem Comm·Kejian ChangXin Xu
Jan 18, 2020·Chemistry : a European Journal·Xiong SunCongqing Zhu
Jan 24, 2020·Chemistry : a European Journal·Nereida HidalgoJesús Campos
Feb 6, 2020·Chemical Communications : Chem Comm·Peter H M BudzelaarLuca Rocchigiani
Dec 20, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexander FriedrichSjoerd Harder
Jun 25, 2021·Chemical Science·Alexander FriedrichSjoerd Harder
Apr 25, 2019·Inorganic Chemistry·Hugh B HamiltonDuncan F Wass
Jun 27, 2018·Inorganic Chemistry·Kejian ChangXin Xu
Sep 14, 2017·Inorganic Chemistry·Md Mamdudur RahmanDmitry V Peryshkov

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