| Title: |
Spectroscopic and Theoretical Studies of Ruthenium Complexes with a Noninnocent N 2 S 2 Ligand in Different Redox States |
| Authors: |
Javier A. Luna; Kyle D. Spielvogel; Nathan R. Loutsch; Sydney M. Loria; Leah P. Weisburn; Mark R. Ringenberg; Bess Vlaisavljevich; Jason M. Keith; Scott K. Shaw; Scott R. Daly |
| Publication Year: |
2025 |
| Collection: |
Erasmus University Rotterdam (EUR): Figshare |
| Subject Terms: |
Biophysics; Biochemistry; Space Science; Environmental Sciences not elsewhere classified; Chemical Sciences not elsewhere classified; underlying electronic structure; square pyramidal complex; ray absorption spectroscopy; first two oxidations; electronic structure investigation; singlet ground state; different oxidation states; crystal xrd data; caspt2 calculations corroborated; l1 |
| Description: |
Herein we report an electronic structure investigation of neutral and oxidized Ru complexes containing a redox noninnocent N 2 S 2 ligand derived from o -phenylenediamide ( L1 ). UV–vis spectroelectrochemistry (SEC) studies were conducted on the square pyramidal complex [Ru II ( L1 )(PPh 3 )] ( 1 ) and the six-coordinate complexes [Ru II (μ-BH 3 )( L1 )(PPh 3 )] ( 2 ) – which has BH 3 bound in a metal–ligand cooperative (MLC) fashion across Ru and L1 – and [Ru II ( L1 )(PPh 3 )(MeCN)] ( 3 ). The SEC results yielded spectra assigned to singly and doubly oxidized 1 and 3 , revealing electronic structure changes as a function of oxidation state and in response to the presence and absence of bound MeCN. By contrast, the SEC results of 2 showed that it rapidly loses MLC-bound BH 3 upon oxidation. The SEC results for 1 and 3 were compared to single-crystal XRD data and UV–vis, EPR, and P K-edge, S K-edge, and Ru L 3 -edge X-ray absorption spectroscopy (XAS) data collected on isolated samples of chemically oxidized 3 . The data revealed that the first two oxidations are primarily localized on the ligand, which was supported by DFT and TDDFT calculations. DFT calculations for the doubly oxidized species revealed a singlet ground state with a singlet–triplet gap of 8.9 kcal/mol. CASPT2 calculations corroborated the DFT calculations and further revealed that the singlet ground state is multiconfigurational with 21% radical character. Collectively, the results establish redox formalisms and the underlying electronic structure of Ru complexes containing a noninnocent tetradentate ligand in different oxidation states. |
| Document Type: |
article in journal/newspaper |
| Language: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Spectroscopic_and_Theoretical_Studies_of_Ruthenium_Complexes_with_a_Noninnocent_N_sub_2_sub_S_sub_2_sub_Ligand_in_Different_Redox_States/29649520 |
| DOI: |
10.1021/acs.inorgchem.5c02059.s001 |
| Availability: |
https://doi.org/10.1021/acs.inorgchem.5c02059.s001; https://figshare.com/articles/journal_contribution/Spectroscopic_and_Theoretical_Studies_of_Ruthenium_Complexes_with_a_Noninnocent_N_sub_2_sub_S_sub_2_sub_Ligand_in_Different_Redox_States/29649520 |
| Rights: |
CC BY-NC 4.0 |
| Accession Number: |
edsbas.395345B |
| Database: |
BASE |