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Unusual Admissions of Guilt: Novel R...

D'Arpino, Alexander Angelo.

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Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands./
Author:	D'Arpino, Alexander Angelo.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2024,
Description:	170 p.
Notes:	Source: Dissertations Abstracts International, Volume: 85-12, Section: B.
Contained By:	Dissertations Abstracts International85-12B.
Subject:	Inorganic chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31235495
ISBN:	9798382840376

Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands.
D'Arpino, Alexander Angelo.

Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands. - Ann Arbor : ProQuest Dissertations & Theses, 2024 - 170 p.

Source: Dissertations Abstracts International, Volume: 85-12, Section: B.

Thesis (Ph.D.)--Cornell University, 2024.

Redox non-innocence (RNI) allows organometallic chemists to impart greater covalency to first row transition metals (TMs) to replicate the reactivity of noble metal congeners. A new, non-innocent tetradentate β-diimine chelate (pddiH2) has been synthesized and coordinated to Cr, Fe, and Co. Treatment of pddiCr with several reagents revealed that cyclopropanation in the ligand backbone could reversibly occur, and several forays into reactivity were conducted. Some exploration into using simple β-diimines as RNI chelates was also performed, generating several new complexes with minimal activity. Another classic example of a redox non-innocent ligand is the nitrosyl. Their electronic ambiguity is well documented, with three redox states available-NO+, NO•, and NO-. The uncertainty in assignment combined with the ligand's spectroscopic handle, ν(NO), allowed for extension of the previously developed system of charge distribution via reporters (CDVR) to M-NO species. First row TM complexes from the Cambridge Structural Database were examined to look for correlations between the calculated charge, cNO, and several metrics, namely d(N-O) and ∠M-N-O. This comparative study allowed for the development of a phenomenological equation of charge for LnM-NO. Several novel mononitrosyl complexes that displayed puzzling and contradictory experimental metrics (e.g. XRD and IR analyses) were also analyzed.

ISBN: 9798382840376Subjects--Topical Terms:

3173556
Inorganic chemistry.
Subjects--Index Terms:

Base metal chemistry

Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands.
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