Understanding the Reactivity of Planar Chiral Naphthindenyl Rhodium(III) Catalysts Open Access

Abstract

In our study, we aimed to explore the impact of extending the aromatic backbone of the indenyl ligand, coupled with modifications to substituents around the Cp moiety, on the reactivity of planar chiral rhodium(III) catalysts. This exploration was geared towards unlocking new possibilities in asymmetric C-H functionalization and catalysis. We hypothesized that introducing a naphthalene backbone in linear and bent configurations would influence the hapticity of the Cp moiety and preference for ring slip due to preferred resonance structures. Despite encountering challenges in synthesizing the naphthindanone precursors to naphthindenes, we successfully synthesized naphthindenyl rhodium(I)-COD and naphthindenyl rhodium(I)-carbonyl species. While we managed to synthesize and purify one rhodium(III) complex, purification challenges remain. We utilized three methods to investigate hapticity, which we correlated with ring slippage. The methods included Tolman electronic parameter analysis, NMR studies, and solid-state structure analysis, which together show a spectrum of hapticities that we correlate with variable levels of ring slippage as a result of the different naphthalene aromatic backbone orientations. Our future work involves completing the rhodium(III) species scope and assessing their reaction rates to understand how the orientation of the naphthalene backbone affects reactivity. We plan to compare the behavior of these catalysts in reactions we have previously developed, aiming to elucidate the effect of modifications in steric profile and electronic asymmetry on reactivity. Additionally, we intend to correlate the various data sets we have accrued with each other and additional data to better characterize hapticity and ring slippage.

Table of Contents

1 - Introduction (1-8)

2 - Results and Discussion (8-35)

2.1 - Ligand Development (8-15)

2.2 - Naphthindenyl Rhodium Complex Development (15-20)

2.3 - Predicting Planar Chiral Naphthindenyl Rhodium(III) Catalyst Reactivity (20-35)

3 - Conclusions and Future Directions (35-37)

4 - Supplemental Information (37-96)

5 - References (97-105)

About this Honors Thesis

Rights statement

• Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.

School	Emory College
Department	Chemistry
Degree	B.S.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Organic
Keyword	Catalysis Organometallics
Committee Chair / Thesis Advisor	Dr. Simon Blakey, Emory University
Committee Members	Dr. Skye Comstra, Emory University Dr. Richard Himes, Emory University Dr. Austin Scharf, Emory University

Last modified

Primary PDF

Thumbnail	Title	Date Uploaded	Actions
	Understanding the Reactivity of Planar Chiral Naphthindenyl Rhodium(III) Catalysts ()	2024-04-10 11:29:05 -0400	Press to Select an action Download

Supplemental Files

Thumbnail	Title	Date Uploaded	Actions