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Development of Homogeneous First Row...

Arizona State University.

Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation.
Author:	Ghosh, Chandrani.
Published:	Ann Arbor : ProQuest Dissertations & Theses, 2018
Description:	354 p.
Notes:	Source: Dissertation Abstracts International, Volume: 80-01(E), Section: B.
Notes:	Adviser: Ryan J. Trovitch.
Contained By:	Dissertation Abstracts International80-01B(E).
Subject:	Inorganic chemistry.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10846542
ISBN:	9780438297319

Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation.
Ghosh, Chandrani.

Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation. - Ann Arbor : ProQuest Dissertations & Theses, 2018 - 354 p.

Source: Dissertation Abstracts International, Volume: 80-01(E), Section: B.

Thesis (Ph.D.)--Arizona State University, 2018.

Transition metals have been extensively employed to address various challenges related to catalytic organic transformations, small molecule activation, and energy storage over the last few decades. Inspired by recent catalytic advances mediated by redox noninnocent pyridine diimine (PDI) and alpha-diimine (DI) ligand supported transition metals, our group has designed new PDI and DI ligands by modifying the imine substituents to feature donor atoms. My doctoral research is focused on the development of PDI and DI ligand supported low valent first row metal complexes (Mn, Fe, Co) and their application in bond activation reactions and the hydrofunctionalization of unsaturated bonds.

ISBN: 9780438297319Subjects--Topical Terms:

708705
Inorganic chemistry.

Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation.
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245 1 0 $a Development of Homogeneous First Row Metal Catalysts (Fe, Mn, Co) for Organic Transformations and Bond Activation.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2018
300 $a 354 p.
500 $a Source: Dissertation Abstracts International, Volume: 80-01(E), Section: B.
500 $a Adviser: Ryan J. Trovitch.
502 $a Thesis (Ph.D.)--Arizona State University, 2018.
520 $a Transition metals have been extensively employed to address various challenges related to catalytic organic transformations, small molecule activation, and energy storage over the last few decades. Inspired by recent catalytic advances mediated by redox noninnocent pyridine diimine (PDI) and alpha-diimine (DI) ligand supported transition metals, our group has designed new PDI and DI ligands by modifying the imine substituents to feature donor atoms. My doctoral research is focused on the development of PDI and DI ligand supported low valent first row metal complexes (Mn, Fe, Co) and their application in bond activation reactions and the hydrofunctionalization of unsaturated bonds.
520 $a First two chapters of this dissertation are centered on the synthesis and application of redox non-innocent ligand supported low valent iron complexes. Notably, reduction of a DI-based iron dibromide led to the formation of a low valent iron dinitrogen compound. This compound was found to undergo a sequential C-H and C-P bond activation processes upon heating to form a dimeric compound. The plausible mechanism for dimer formation is also described here.
520 $a Inspired by the excellent carbonyl hydrosilylation activity of our previously reported Mn catalyst, (Ph2PPrPDI)Mn, attempts were made to synthesize second generation Mn catalyst, which is described in the third chapter. Reduction of (PyEtPDI)MnCl2 furnished a deprotonated backbone methyl group containing Mn compound [(PyEt PDEA)Mn] whereas reduction of (Ph2PEtPDI)MnCl 2 produced a dimeric compound, [(Ph2PEtPDI)Mn] 2. Both compounds were characterized by NMR spectroscopy and XRD analysis. Hydrosilylation of aldehydes and ketones have been studied using [( PyEtPDEA)Mn] as a pre-catalyst. Similarly, 14 different aldehydes and 6 different ii formates were successfully hydrosilylated using [( Ph2PEtPDI)Mn]2 as a pre-catalyst.
520 $a Encouraged by the limited number of cobalt catalysts for nitrile hydroboration, we sought to develop a cobalt catalyst that is active for hydroboration under mild conditions, which is discussed in the last chapter. Treatment of ( PyEtPDI)CoCl2 with excess NaEt3BH furnished a diamagnetic Co(I) complex [(PyEtPDIH)Co], which exhibits a reduced imine functionality. Having this compound characterized, a broad substrate scope for both nitriles and imines have been investigated. The operative mechanism for nitrile dihydroboration has been investigated based on the outcomes of a series of stoichiometric reactions using NMR spectroscopy.
590 $a School code: 0010.
650 4 $a Inorganic chemistry. $3 708705
650 4 $a Chemistry. $3 188628
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710 2 $a Arizona State University. $b Chemistry. $3 826973
773 0 $t Dissertation Abstracts International $g 80-01B(E).
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791 $a Ph.D.
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