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Solving a 50-Year-Old Mystery: Synth...

Paul, Sanchita,

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Solving a 50-Year-Old Mystery: Synthesis of Mn(III) Halide Phosphine Compounds, and Other Quests With Three-Coordinate Zn(II) Compounds /

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Solving a 50-Year-Old Mystery: Synthesis of Mn(III) Halide Phosphine Compounds, and Other Quests With Three-Coordinate Zn(II) Compounds // Sanchita Paul.
作者:	Paul, Sanchita,
面頁冊數:	1 electronic resource (186 pages)
附註:	Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
Contained By:	Dissertations Abstracts International86-03B.
標題:	Chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31555520
ISBN:	9798384091929

Solving a 50-Year-Old Mystery: Synthesis of Mn(III) Halide Phosphine Compounds, and Other Quests With Three-Coordinate Zn(II) Compounds /
Paul, Sanchita,

Solving a 50-Year-Old Mystery: Synthesis of Mn(III) Halide Phosphine Compounds, and Other Quests With Three-Coordinate Zn(II) Compounds /Sanchita Paul. - 1 electronic resource (186 pages)

Source: Dissertations Abstracts International, Volume: 86-03, Section: B.

The ability of transition metal compounds with various ligands to form stable yet reactive compounds is fundamental to their versatility. This dissertation work aims to advance our understanding on the synthesis and reactivity of high-valent manganese phosphine and low-coordinate zinc alkyl compounds. The first project originated from a retrosynthetic analysis of Grubbs' Gen I RuIV -(PR3) alkylidene and Jia's ReV -(PR3) alkylidyne that revealed [MnIIIX3(PR3)2] complexes as a potential starting material. The attempts to synthesize these MnIIIX3 phosphine complexes began nearly 50 years ago by McAullife and co-workers. However, the dearth of viable methods to prepare them is the reason behind their negligible utility in literature. Our work solved this issue by preparing some known and novel [MnIIIX3(PR3)2] (X= Cl, Br, I; R = Me, nBu) complexes with robust synthetic strategies. This work further introduces a unique P-Cl bond formation reaction, and solves a few controversial aspects regarding the formation of [MnIIIX2(PR3)(O2)] adducts from aerobic oxidation of [MnIIX2(PR3)n] complexes.In addition to the chemistry of MnIIIX3 with phosphines, this work explores the utility of PN ligands for isolation of low-coordinate zinc complexes as well, and a comparative catalytic hydrogenation of polar substrates. It takes inspiration from Milstein's 2020 study (J. Am. Chem. Soc. 2020, 142, 34, 14513) where he demonstrated H2 activation via the traditional metal-ligand cooperativity mechanism followed by catalytic hydrogenation with PNP-Zn(II) complexes. Milstein's Zn(II) systems proved to be more effective than the previously reported Zn hydrogenation catalysts, and exhibited a trailing hemilabile phosphorus arm. We hypothesized that removal of this third arm would increase access to the Zn site and enhance catalytic activity. Indeed, we successfully validated our hypothesis with bidentate PN-Zn amido- and alkyl-complexes. Moreover, our collective experimental and theoretical results prompted us to propose a novel mechanism that aligns well with the substantial work conducted in the group 2 hydrogenation catalysis area.Lastly, a brief and final chapter of this dissertation details a novel strategy that can be employed for the isolation of homoleptic lithium trialkyzincates.

English

ISBN: 9798384091929Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Ligands

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520 $a The ability of transition metal compounds with various ligands to form stable yet reactive compounds is fundamental to their versatility. This dissertation work aims to advance our understanding on the synthesis and reactivity of high-valent manganese phosphine and low-coordinate zinc alkyl compounds. The first project originated from a retrosynthetic analysis of Grubbs' Gen I RuIV -(PR3) alkylidene and Jia's ReV -(PR3) alkylidyne that revealed [MnIIIX3(PR3)2] complexes as a potential starting material. The attempts to synthesize these MnIIIX3 phosphine complexes began nearly 50 years ago by McAullife and co-workers. However, the dearth of viable methods to prepare them is the reason behind their negligible utility in literature. Our work solved this issue by preparing some known and novel [MnIIIX3(PR3)2] (X= Cl, Br, I; R = Me, nBu) complexes with robust synthetic strategies. This work further introduces a unique P-Cl bond formation reaction, and solves a few controversial aspects regarding the formation of [MnIIIX2(PR3)(O2)] adducts from aerobic oxidation of [MnIIX2(PR3)n] complexes.In addition to the chemistry of MnIIIX3 with phosphines, this work explores the utility of PN ligands for isolation of low-coordinate zinc complexes as well, and a comparative catalytic hydrogenation of polar substrates. It takes inspiration from Milstein's 2020 study (J. Am. Chem. Soc. 2020, 142, 34, 14513) where he demonstrated H2 activation via the traditional metal-ligand cooperativity mechanism followed by catalytic hydrogenation with PNP-Zn(II) complexes. Milstein's Zn(II) systems proved to be more effective than the previously reported Zn hydrogenation catalysts, and exhibited a trailing hemilabile phosphorus arm. We hypothesized that removal of this third arm would increase access to the Zn site and enhance catalytic activity. Indeed, we successfully validated our hypothesis with bidentate PN-Zn amido- and alkyl-complexes. Moreover, our collective experimental and theoretical results prompted us to propose a novel mechanism that aligns well with the substantial work conducted in the group 2 hydrogenation catalysis area.Lastly, a brief and final chapter of this dissertation details a novel strategy that can be employed for the isolation of homoleptic lithium trialkyzincates.
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