Issue 21, 2024

Local force constants and charges of the nitrosyl ligand in photoinduced NO linkage isomers in a prototypical ruthenium nitrosyl complex

Abstract

Photoinduced linkage isomers (PLI) of the NO ligand in transition-metal nitrosyl compounds can be identified by vibrational spectroscopy due to the large shifts of the [small nu, Greek, tilde](NO) stretching vibration. We present a detailed experimental and theoretical study of the prototypical compound K2[RuCl5NO], where [small nu, Greek, tilde](NO) shifts by ≈150 cm−1 when going from the N-bound (κN) ground state (GS) to the oxygen-bound (κO) metastable linkage isomer MS1, and by ≈360 cm−1 when going to the side-on (κ2N,O) metastable linkage isomer MS2. We show that the experimentally observed N–O stretching modes of the GS, MS1, and MS2 exhibit strong coupling with the Ru–N and Ru–O stretching modes, which can be decoupled using the local mode vibrational theory formalism. From the resulting decoupled pure two-atomic harmonic oscillators the local force constants are determined, which all follow the same quadratic behavior on the wavenumber. A Bader charge analysis shows that the total charge on the NO ligand is not correlated to the observed frequency shift of [small nu, Greek, tilde](NO).

Graphical abstract: Local force constants and charges of the nitrosyl ligand in photoinduced NO linkage isomers in a prototypical ruthenium nitrosyl complex

Supplementary files

Article information

Article type
Paper
Submitted
03 ⵉⴱⵔ 2024
Accepted
03 ⵎⴰⵢ 2024
First published
06 ⵎⴰⵢ 2024

Phys. Chem. Chem. Phys., 2024,26, 15255-15267

Local force constants and charges of the nitrosyl ligand in photoinduced NO linkage isomers in a prototypical ruthenium nitrosyl complex

A. A. Mikhailov, A. Gansmüller, K. A. Konieczny, S. Pillet, G. Kostin, P. Klüfers, T. Woike and D. Schaniel, Phys. Chem. Chem. Phys., 2024, 26, 15255 DOI: 10.1039/D4CP01374C

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