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Development of Phosphinoamide-Suppor...

Gramigna, Kathryn Marie.

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Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation./
Author:	Gramigna, Kathryn Marie.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2019,
Description:	219 p.
Notes:	Source: Dissertation Abstracts International, Volume: 80-08(E), Section: B.
Contained By:	Dissertation Abstracts International80-08B(E).
Subject:	Inorganic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=13427339
ISBN:	9781392020517

Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation.
Gramigna, Kathryn Marie.

Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation. - Ann Arbor : ProQuest Dissertations & Theses, 2019 - 219 p.

Source: Dissertation Abstracts International, Volume: 80-08(E), Section: B.

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

Homo- and heterobimetallic complexes featuring a polar metal-metal bond are well poised for activation of small molecules via cooperative bond activation reactions, allowing for reactivity inaccessible to analogous monometallic systems. Installing Fe and Co centers into a tris(phosphinoamide) ligand framework affords a series of highly stable late metal bimetallic complexes whose structural, electronic, and magnetic properties have been studied in detail, and the reactivity of these systems has been explored. By changing the late metal centers, the electronics of the system is perturbed, in some cases affecting the metal-metal bonding and the reactivity of the complexes. In particular, the reactivity of imido-bound bimetallics toward nitrene transfer varies depending predominantly on the extent of metal-metal bonding. Reactivity is hindered by increasing metal-metal bond strength and is best promoted in complexes lacking a direct metal-metal interaction. The synthesis, electronic and structural characterization, and reactivity of a series of homo- and heterobimetallic Fe and Co systems shed light on the nature of the metal-metal interaction between two first row late transition metals.

ISBN: 9781392020517Subjects--Topical Terms:

3173556
Inorganic chemistry.

Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation.
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100 1 $a Gramigna, Kathryn Marie. $3 3430881
245 1 0 $a Development of Phosphinoamide-Supported Homo- and Heterobimetallic Complexes Featuring Metal-Metal Bonds toward Cooperative Small Molecule Activation.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2019
300 $a 219 p.
500 $a Source: Dissertation Abstracts International, Volume: 80-08(E), Section: B.
500 $a Adviser: Christine M. Thomas.
502 $a Thesis (Ph.D.)--Brandeis University, 2019.
520 $a Homo- and heterobimetallic complexes featuring a polar metal-metal bond are well poised for activation of small molecules via cooperative bond activation reactions, allowing for reactivity inaccessible to analogous monometallic systems. Installing Fe and Co centers into a tris(phosphinoamide) ligand framework affords a series of highly stable late metal bimetallic complexes whose structural, electronic, and magnetic properties have been studied in detail, and the reactivity of these systems has been explored. By changing the late metal centers, the electronics of the system is perturbed, in some cases affecting the metal-metal bonding and the reactivity of the complexes. In particular, the reactivity of imido-bound bimetallics toward nitrene transfer varies depending predominantly on the extent of metal-metal bonding. Reactivity is hindered by increasing metal-metal bond strength and is best promoted in complexes lacking a direct metal-metal interaction. The synthesis, electronic and structural characterization, and reactivity of a series of homo- and heterobimetallic Fe and Co systems shed light on the nature of the metal-metal interaction between two first row late transition metals.
520 $a Introduction of an early metal (Zr) and a late metal (Co) into a bis(phosphinoamide) ligand framework generates a significantly more reactive complex capable of facile H2 activation. A highly reduced Zr/Co complex features a strongly polarized metal-metal triple bond, which plays an intergral part in substrate activation and in the stabilization of the bimetallic transformations. The Zr/Co bimetallic complex catalyzes the hydrogenation of alkenes and the semi-hydrogenation of alkynes, and relevant intermediates identified in situ have been isolated and structurally characterized.
520 $a An understanding of the reactivity of the bis(phosphinoamide) Zr/Co complex was expanded by exploring the activation of polar substrates. The bimetallic complex was found to catalytically dehydrogenate ammonia borane and facilitate transfer hydrogenation to styrene. Furthermore, the reactivity exhibited towards ketones may elucidate the ways in which early/late heterobimetallics activate C=O bonds and how substrate access to the metal-metal bond may change reaction pathways. These findings lend insight into the roles that metal-metal bonding and cooperativity play in the activation of small molecules and subsequent catalytic transformations.
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650 4 $a Inorganic chemistry. $3 3173556
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