Structure

Formation of Ru Metal Complexes From (-)-1,2-Bis{(s)-4-isopropyl-4,5-dihydro-oxazol-2-yl]benzene ligand varieties: A Computational Approach

jpark189 CURE Projects, Spring 2020 , , , ,

Class: CHEM 0500 – Inorganic Chemistry 

Instructor(s): Dr. Eric Victor

Student(s): Keerthi Sreenivasan (Chemistry ’21), Sophia Zheng, Laura Perlmutter, Allison Lin, Veronica Gordon

“This poster includes generated data calculations and analysis of the notable properties of the ligands as they change after bonding to the Ru metal center.”

–Keerthi Sreenivasan

Description: 

Based on an existing protocol for synthesizing 2,6-bis[(S)-isopropyl-4,5-dihydro-oxazol-2-yl]- thiobenzene by Peer et. al, we tested a novel microwave synthesis protocol aimed at shortening the 3-5 day synthesis time. After two rounds of testing microwave synthesis, characterization of the product using GC-MS was inconclusive, and future refinement of the microwave synthesis protocol is necessary. Due to the transition to remote work, we then moved to computational work on the ligand and two modified versions. Calculations were performed to determine structural parameters of the ligands, simulations of spectroscopy and orbital images. A second round of calculations was done while binding the ligands in a tridentate fashion to a ruthenium metal complex. Reactive nitrogen oxide species have been shown to play a significant role in biological processes, and various metal complexes show reactivity with SNO and SSNO anions. In this CURE project, we were able to learn how to perform novel synthetic methods for a ruthenium complex using published ligands and characterize them using computational software.

Remote-Learning Ruthenium (II) Complexes

jpark189 CURE Projects, Spring 2020 , , , ,

 

Class: CHEM 0500 – Inorganic Chemistry 

Instructor(s): Dr. Eric Victor 

Student(s): Jon Mallen (Biophysics Sc.B. ’22), Yolanda Candler, Myung Joo Lee, Nicholas Moreno, Vivian Yuen

”My opinion about research at Brown has only been improved. Learning about bacteriophages in my first year and discovering my own, and now taking part in the Inorganic Chemistry CURE last semester, has confirmed my affinity for laboratory research, and also allowed me to better pinpoint my interests, skills, and weaknesses.”

–John Mallen

Description: 

We computationally developed, optimized, and extracted energetic and physical parameters for the structures of eight novel benzothiazole alkimazole ruthenium (II) complexes through the Avogadro and ORCA software packages. Four complexes employed a benzothiazole methimazole ligand that was bound to the ruthenium (II) with either syn or anti sulfur-sulfur coordination in either the fac or mer geometry, and the other four employed a benzothiazole isopropimazole with the same syn/anti and fac/mer variation as its methimazole counterpart. There is no clear preference for coordination site and geometry among the different methimazole and isopropimazole in each of their four comparitive structures. However, the small difference in alkyl side-chain between the methimazole and isopropimazole has a significant effect on the resulting energetics of the involved complexes, with the isopropimazole variants uniformly more lower in energy than the methimazole complexes. This is evidence of greater trends in the complexation of ruthenium (II) with benzothiazole alkimazole ligands and is thus a part of the empirical data that will contribute to the future design of chemical routes employing this class of molecules.