Campus Access Only
All rights reserved. This publication is intended for use solely by faculty, students, and staff of University of the Pacific. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, now known or later developed, including but not limited to photocopying, recording, or other electronic or mechanical methods, without the prior written permission of the author or the publisher.
Date of Award
Thesis - Pacific Access Restricted
Master of Science (M.S.)
Pharmaceutical and Chemical Sciences
First Committee Member
Second Committee Member
Dirhodium complexes have been known for their catalytic reactivities toward C-H bond activation for nearly two decades. However, both experimental and theoretical studies have not given a clear explanation on the roles of each metal in the reactivities, largely due to the limited number of available bimetallic species. To study the system systematically, we set our goal to synthesize bimetallic complexes from two independent approaches. In the first approach, five N, N’ -diarylformamidines with symmetric or asymmetric substituents on the phenyl groups were synthesized and fully characterized. Formamidines without bulky substituents exhibited fluxionality in solution, which was proved by a single set of signal in 1 H NMR. In contrast, two sets of signals were observed for formamidines with bulky substituents in the ortho positions, indicating two major stereoisomers ( E and Z conformers) co-existing in solution. In solid state, strong stability for E conformers was gained from a pair of H bonds between two ligands facing each other. The phenomenon was observed for all ligands but N, N’ -bis(2,6-dimethylphenyl)formamidine ( L2 ), in which ligands in Z conformation were connected through H bonds from both sides of a ligand and an infinite chain structure formed in solid state. Metallation of the formamidines with diethylzinc and mesitylmagnesium bromide produced ten complexes in a variety of geometries, indicating a rich diversity in geometry for the formamidine family as coordination ligands. Among these complexes, three bimetallic complexes, with metal atoms close in distance, are potential candidates for the formation of complexes with metal-metal bonds. In each dizinc complex, two formamidinates (deprotonated formamidines) spanned over the two Zn atoms and brought them together, while in the dimagnesium complex, the two Mg atoms were bridged by two bromides, resulting in a Mg 2 Br 2 cubic core. In the other approach, two newly designed tripodal ligands were obtained at relatively high yields. Each of the ligands contains three branches built up from a central atom C or N. Lone pairs on the three branches of a deprotonated ligand working together could behave like a three-prong clamp and secure two metal centers closely in the pocket. A dichromium complex with a geometry matching our initial design was successfully synthesized. Meanwhile, two monometallic complexes, potential candidates as precursors to heterobimetallic complexes, were obtained.
Tsai, Yi-Ju. (2014). Two approaches to the design and synthesis of bimetallic complexes. University of the Pacific, Thesis - Pacific Access Restricted. https://scholarlycommons.pacific.edu/uop_etds/272
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
To access this thesis/dissertation you must have a valid pacific.edu email address and log-in to Scholarly Commons.Find in ProQuest
If you are the author and would like to grant permission to make your work openly accessible, please email
In Copyright. URI: http://rightsstatements.org/vocab/InC/1.0/
This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).