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Transition Metal Complexes for Challenging Reductive Transformations: From Nitrogen Fixation Catalysts to Photoreductants

Citation

Fajardo, Javier, Jr. (2020) Transition Metal Complexes for Challenging Reductive Transformations: From Nitrogen Fixation Catalysts to Photoreductants. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0fgd-j835. https://resolver.caltech.edu/CaltechTHESIS:06082020-141438135

Abstract

Transition metal complexes are routinely employed as catalysts for the reductive cleavage of a diverse array of strong chemical bonds. Two notable research areas that exemplify such utility are nitrogen fixation, involving cleavage of the notoriously unreactive triple bond of dinitrogen (N₂) to form ammonia (NH₃), and photoredox catalysis, wherein powerful photoreductants generated by visible light excitation facilitate challenging reduction steps in a host of synthetic organic transformations. This thesis focuses on a number of structure-function studies conducted on group 8 transition metal complexes that catalyze N₂-to-NH₃ conversion, commonly referred to as the nitrogen reduction reaction (N₂RR), and on homoleptic tungsten(0) arylisocyanides that, among their many attractive qualities, possess highly reducing electronically excited states. These comparative studies provide fundamental insight into critical design features which can guide efforts to improve existing N₂RR or photocatalysts or rationally tailor them for specific applications.

Chapter 2 details the effect apical Lewis acidic atom substitution in P₃XFe platforms (X = B, Al, Ga) has on structure, bonding, and N₂RR activity. Structural, spectroscopic, electrochemical, and computational studies reveal that all three P₃XFe systems possess similar electronic structures, degrees of N₂ activation, and geometric flexibility, but P₃AlFe and P₃GaFe display significantly lower N₂RR efficiencies than P₃BFe when treated with HBArF₄/KC₈ or [H₂NPh₂][OTf]/Cp*₂Co at –78 °C in Et₂O.

Chapter 3 reports on isostructural tris(phosphino)silyl Ru and Os complexes that mediate catalytic N₂RR. The study of the homologous, isostructural series of complexes P₃SiM (M = Fe, Ru, Os) helps delineate important factors for N₂RR catalyst design. Low-temperature protonation of P₃SiOs–N₂⁻ yields P₃SiOs=NNH₂⁺, representing the first instance of an Os–N₂ species being converted to a protonated Os–NxHy product.

Chapter 4 communicates a novel series of homoleptic tungsten(0) photoactive complexes supported by fused-ring (CN-1-(2-iPr)-Naph) or alkynyl-bridged (CNDippCCAr) arylisocyanide ligands. Systematic studies establish facile electronic variation of the CNDippCCAr platform as a straightforward method by which to rationally modulate the ground- and excited-state properties of W(CNDippCCAr)₆ complexes. The photophysical properties of W(CN-1-(2-iPr)-Naph)₆ reveal potential benefits of utilizing fused-ring arylisocyanide ligands in the design of this class of photosensitizers.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Catalysis; photosensitizers; nitrogen fixation; nitrogen reduction; arylisocyanides; tungsten arylisocyanides; osmium; ruthenium; metal-to-ligand charge transfer; luminescence; photophysics; photochemistry; photoreductants
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Restricted to Caltech community only
Research Advisor(s):
  • Gray, Harry B.
Thesis Committee:
  • Agapie, Theodor (chair)
  • Peters, Jonas C.
  • Miller, Thomas F.
  • Gray, Harry B.
Defense Date:2 June 2020
Non-Caltech Author Email:jfajardo101 (AT) gmail.com
Record Number:CaltechTHESIS:06082020-141438135
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:06082020-141438135
DOI:10.7907/0fgd-j835
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.7b10204DOIArticle adapted for Chapter 3.
ORCID:
AuthorORCID
Fajardo, Javier, Jr.0000-0003-0612-7953
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13794
Collection:CaltechTHESIS
Deposited By: Javier Fajardo Jr.
Deposited On:09 Jun 2020 00:30
Last Modified:15 Dec 2020 01:52

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