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Redox-Active Pincer Ligands on Chrom...

Labrum, Nicholas Scott.

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Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine./
作者:	Labrum, Nicholas Scott.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2019,
面頁冊數:	210 p.
附註:	Source: Dissertation Abstracts International, Volume: 80-09(E), Section: B.
Contained By:	Dissertation Abstracts International80-09B(E).
標題:	Inorganic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=13877873
ISBN:	9781392148976

Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine.
Labrum, Nicholas Scott.

Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine. - Ann Arbor : ProQuest Dissertations & Theses, 2019 - 210 p.

Source: Dissertation Abstracts International, Volume: 80-09(E), Section: B.

Thesis (Ph.D.)--Indiana University, 2019.

Technological societies have seen a substantial increase in the consumption of carbon-based fuels since the onset of the industrial revolution. This has created an inexhaustible carbon reserve in refractory CO2 with no efficient strategy for carbon recycling. This work describes how a multifunctional ligand scaffold was studied alongside chromium, a metal that is often overlooked in CO2 reductive processes. Divalent chromium, Cr[N(SiMe3)2]2(THF)2, served as an attractive starting material to leverage acidic proton in bis-(pyrazolyl)pyridine, H2L, to accomplish a goal of pre-organized metal complex for CO2 transformation. Indeed, the reaction of Cr[N(SiMe3)2]2(THF)2 with H2L led to the formation of oligomeric CrII products, including a rare tetra-chromium complex, [CrL]4, with up to four reducing equivalents pre-loaded. Chemically reduced [CrL]2 reacts with CO2 within five minutes to produce CO and CO32-. This work ultimately establishes that chemically reduced Cr supported by L2- is competent for CO2 reduction.

ISBN: 9781392148976Subjects--Topical Terms:

3173556
Inorganic chemistry.

Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine.
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245 1 0 $a Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2019
300 $a 210 p.
500 $a Source: Dissertation Abstracts International, Volume: 80-09(E), Section: B.
500 $a Adviser: Kenneth G. Caulton.
502 $a Thesis (Ph.D.)--Indiana University, 2019.
520 $a Technological societies have seen a substantial increase in the consumption of carbon-based fuels since the onset of the industrial revolution. This has created an inexhaustible carbon reserve in refractory CO2 with no efficient strategy for carbon recycling. This work describes how a multifunctional ligand scaffold was studied alongside chromium, a metal that is often overlooked in CO2 reductive processes. Divalent chromium, Cr[N(SiMe3)2]2(THF)2, served as an attractive starting material to leverage acidic proton in bis-(pyrazolyl)pyridine, H2L, to accomplish a goal of pre-organized metal complex for CO2 transformation. Indeed, the reaction of Cr[N(SiMe3)2]2(THF)2 with H2L led to the formation of oligomeric CrII products, including a rare tetra-chromium complex, [CrL]4, with up to four reducing equivalents pre-loaded. Chemically reduced [CrL]2 reacts with CO2 within five minutes to produce CO and CO32-. This work ultimately establishes that chemically reduced Cr supported by L2- is competent for CO2 reduction.
520 $a The coordination of carbonate between two chromium atoms within the [CrL]2 framework prompted the study of other Lewis bases (Cl-, O2-, DMAP) to form a broad range of [Cr2L2(mu2-E)] and [CrL(E)2] species. Weak acids were then targeted to demonstrate the proton responsiveness of the deprotonated bis-(pyrazolate)pyridine pincer ligand. The conjugate base of HX was found to have similar reactivity to the studied Lewis bases.
520 $a In addition, we sought to exploit the reducing power and Bronsted basicity of this compact package, [CrL]2, in bond scission of the substrate and thus targeted the reductively promoted disproportionation of hydrazine. Treatment of [CrL]2 with phenylhydrazine results in the formation of [Cr2L2(PhNH2)2(PhHNN)] accompanied by the generation of benzene, N2, and NH3. The presence of an N-C bond in the chosen phenylhydrazine allowed for isolation of the PhHNN2- moiety. Next, the ability of [CrL]2 to act as an electron shuttle for N=N and C=O bond reduction was investigated using azobenzene, benzo[c]cinnoline, and 3,5-ditertbutylbenzoquinone. The extent of reduction (one- and two-electron reduction and full N-N bond scission) and the resulting charge on these ligands will be discussed.
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