國立高雄大學圖資館 |

語系: 繁體中文

說明(常見問題)

圖資館首頁

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

Investigating the C–H Bond Activatio...

Carroll, Timothy Gary.

Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes.
作者:	Carroll, Timothy Gary.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, 2020
面頁冊數:	234 p.
附註:	Source: Dissertations Abstracts International, Volume: 82-05, Section: B.
附註:	Advisor: Menard, Gabriel.
Contained By:	Dissertations Abstracts International82-05B.
標題:	Chemistry.
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28092669
ISBN:	9798684682018

Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes.
Carroll, Timothy Gary.

Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 234 p.

Source: Dissertations Abstracts International, Volume: 82-05, Section: B.

Thesis (Ph.D.)--University of California, Santa Barbara, 2020.

This item must not be sold to any third party vendors.

Alkanes, or saturated hydrocarbons, have long been zealously exploited for their energy content through combustion processes; however, practical processes for converting them directly to higher value commodity chemicals remain limited. This stems from the inherent inertness of alkanes and the subsequent difficulty in activating their strong and localized C–C and C–H bonds. The introduction of functionality into unactivated C–H bonds incites many practical advantages – from offering new methodologies for fine chemical synthesis, to far-reaching implications of replacing our current alkane petrochemical feedstocks. For the past several decades, there has been tremendous work in utilizing transition-metal complexes to activate inert C–H ¬bonds and install functionality under mild conditions. While profitable practical applications remain a long-term goal, our mechanistic understanding of these transition-metal mediated transformations has advanced tremendously, and has provided a framework to recognize new strategies for useful C–H bond activation.For example, recent computational studies suggest that the phosphate support in the commercial vanadium phosphate oxide (VPO) catalyst – used for the partial oxidation of butane to maleic anhydride – may play a critical role in initiating butane C–H bond activation through a mechanism termed reduction-coupled oxo activation (ROA), similar to proton-coupled electron transfer (PCET); however, there has been a general lack of experimental evidence to support this mechanism. Herein, we present a wide library of molecular model compounds to examine the validity of the proposed ROA mechanism, which incites C–H bond activation through a main-group/transition metal cooperative mechanism. We report the synthesis, characterization, and reactivity of a series of mono/multi-metallic vanadium phosphate complexes, including the first experimental evidence supporting the proposed ROA mechanism using 1,4-(bistrimethylsilyl)-pyrazine as a “bulky hydrogen” surrogate. Detailed analyses of possible reaction pathways, involving the isolation and full characterization of potential step-wise intermediates, as well as the determination of minimum experimentally and computationally derived thermochemical values are described. Additionally, ongoing work has shown that careful electronic tuning of these vanadium phosphate complexes can enable enhanced reactivity towards weak C–H bonds.

ISBN: 9798684682018Subjects--Topical Terms:

188628
Chemistry.
Subjects--Index Terms:

C-H Activation

Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes.
LDR:03658nmm a2200361 4500 001 594621
005 20210521101710.5
008 210917s2020 ||||||||||||||||| ||eng d
020 $a 9798684682018
035 $a (MiAaPQ)AAI28092669
035 $a AAI28092669
040 $a MiAaPQ $c MiAaPQ
100 1 $a Carroll, Timothy Gary. $3 886665
245 1 0 $a Investigating the C–H Bond Activation Mechanism at Phosphorus(V) Oxides Using Vanadium Phosphorus Oxide (VPO) Model Complexes.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2020
300 $a 234 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-05, Section: B.
500 $a Advisor: Menard, Gabriel.
502 $a Thesis (Ph.D.)--University of California, Santa Barbara, 2020.
506 $a This item must not be sold to any third party vendors.
520 $a Alkanes, or saturated hydrocarbons, have long been zealously exploited for their energy content through combustion processes; however, practical processes for converting them directly to higher value commodity chemicals remain limited. This stems from the inherent inertness of alkanes and the subsequent difficulty in activating their strong and localized C–C and C–H bonds. The introduction of functionality into unactivated C–H bonds incites many practical advantages – from offering new methodologies for fine chemical synthesis, to far-reaching implications of replacing our current alkane petrochemical feedstocks. For the past several decades, there has been tremendous work in utilizing transition-metal complexes to activate inert C–H ¬bonds and install functionality under mild conditions. While profitable practical applications remain a long-term goal, our mechanistic understanding of these transition-metal mediated transformations has advanced tremendously, and has provided a framework to recognize new strategies for useful C–H bond activation.For example, recent computational studies suggest that the phosphate support in the commercial vanadium phosphate oxide (VPO) catalyst – used for the partial oxidation of butane to maleic anhydride – may play a critical role in initiating butane C–H bond activation through a mechanism termed reduction-coupled oxo activation (ROA), similar to proton-coupled electron transfer (PCET); however, there has been a general lack of experimental evidence to support this mechanism. Herein, we present a wide library of molecular model compounds to examine the validity of the proposed ROA mechanism, which incites C–H bond activation through a main-group/transition metal cooperative mechanism. We report the synthesis, characterization, and reactivity of a series of mono/multi-metallic vanadium phosphate complexes, including the first experimental evidence supporting the proposed ROA mechanism using 1,4-(bistrimethylsilyl)-pyrazine as a “bulky hydrogen” surrogate. Detailed analyses of possible reaction pathways, involving the isolation and full characterization of potential step-wise intermediates, as well as the determination of minimum experimentally and computationally derived thermochemical values are described. Additionally, ongoing work has shown that careful electronic tuning of these vanadium phosphate complexes can enable enhanced reactivity towards weak C–H bonds.
590 $a School code: 0035.
650 4 $a Chemistry. $3 188628
650 4 $a Inorganic chemistry. $3 708705
653 $a C-H Activation
653 $a Organometallic
653 $a Phosphates
653 $a Vanadium
653 $a VPO catalyst
690 $a 0485
690 $a 0488
710 2 $a University of California, Santa Barbara. $b Chemistry. $3 730268
773 0 $t Dissertations Abstracts International $g 82-05B.
790 $a 0035
791 $a Ph.D.
792 $a 2020
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28092669