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Electrophilic Fluorophosphonium Cati...

Caputo, Christopher Blain.

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Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry./
作者:	Caputo, Christopher Blain.
面頁冊數:	237 p.
附註:	Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.
Contained By:	Dissertation Abstracts International76-12B(E).
標題:	Chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3715647
ISBN:	9781321939040

Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry.
Caputo, Christopher Blain.

Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry. - 237 p.

Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.

Thesis (Ph.D.)--University of Toronto (Canada), 2015.

Catalytic transformations are of utmost importance for the synthesis of goods and materials. Transition metal systems have traditionally been employed for catalytic processes, however this notion has begun to change with the renaissance in metal-free catalysts. One subset of metal-free catalysis is frustrated Lewis pairs (FLPs). These are combinations of Lewis acids and Lewis bases that are precluded from generating classical adducts due to steric encumbrance. This thesis expands the scope of FLP reactivity by investigating the chemistry with novel Lewis bases, acids and substrates.

ISBN: 9781321939040Subjects--Topical Terms:

516420
Chemistry.

Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry.
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245 1 0 $a Electrophilic Fluorophosphonium Cations - The Transition from Boron to Phosphorus Lewis Acids in Frustrated Lewis Pair Chemistry.
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500 $a Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.
500 $a Adviser: Douglas W. Stephan.
502 $a Thesis (Ph.D.)--University of Toronto (Canada), 2015.
520 $a Catalytic transformations are of utmost importance for the synthesis of goods and materials. Transition metal systems have traditionally been employed for catalytic processes, however this notion has begun to change with the renaissance in metal-free catalysts. One subset of metal-free catalysis is frustrated Lewis pairs (FLPs). These are combinations of Lewis acids and Lewis bases that are precluded from generating classical adducts due to steric encumbrance. This thesis expands the scope of FLP reactivity by investigating the chemistry with novel Lewis bases, acids and substrates.
520 $a Sterically unencumbered amines form Lewis acid base adducts with B(C 6F5)3. These amines were encapsulated into a [2]rotaxane in order to impart steric protection without covalent modifications. These combinations were shown to activate H2 in an FLP manner and led to the discovery of an oxygen/boron hydrogenation catalyst.
520 $a Phosphorus/boron FLPs were reacted with a variety of fluoroalkanes resulting in the activation of the C-F bond. From this it was shown that B(C6F 5)3 can act as a competent hydrodefluorination catalyst for fluoroalkanes. The reactions of P/B FLP systems with XeF2 were also explored, resulting in the formation of fluorophosphonium fluoroborate salts. This led to the discovery of highly electrophilic fluorophosphonium cations.
520 $a Organophosphorus compounds are best known for their roles as Lewis bases. Considerably less attention has been paid to Lewis acidic phosphonium cations. The reactivity of these EPCs is described herein. They have found applications in CO2 sequestration, catalytic C-F bond activation, hydrosilylation, dehydrocoupling and transfer hydrogenation reactions. Finally, they have shown promise in FLP chemistry, with preliminary results indicating they are capable of acting as a Lewis acid for H2 activation.
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