TY - JOUR

T1 - Solvent-assisted substitution of chloro‑ligands by N-heterocycles in ruthenium nitrosyl complex

AU - Stolyarova, Elena D.

AU - Eltsov, Ilia V.

AU - Sukhikh, Taisiya S.

AU - Kostin, Gennadiy A.

PY - 2026/1/15

Y1 - 2026/1/15

N2 - The mechanism of solvent-assisted ligand substitution in a DMF solution of [RuNOCl5]2- with pyridine-based heterocycles (L) was determined by NMR (15N, 1H) technique. The first substitution stage corresponds to the formation of trans-(NO, DMF)-[RuNOCl4(DMF)]−, which undergoes further substitution with the formation of cis,trans-(NO, L)-[RuNOCl4L]− complexes. The formation of di-substituted products [RuNOCl3L2] depends on the nature of the starting [RuNOCl5]2- salt. For ((C4H9)4N)2[RuNOCl5] the reaction with a 6-7 molar excess of L results mainly in the mixture of cis- andtrans-(NO, L)-[RuNOCl4L]− in the temperature range of 80–140 °C. On the contrary, the reaction of K2[RuNOCl5] with a 6–7 molar excess of L (140 °C, 40–60 min) results mainly in trans-(L, L)-[RuNOCl3L2] (60 %), while other products do not exceed 10–15 % each. The difference was explained by the removal of chloride ions from the DMF solution in the form of KCl. The structure of intermediates and final products in solution was determined based on NMR data. Additionally, some intermediate products with different pyridine-based heterocycles were isolated as individual crystals, and the structures of trans-(NO, DMF)-[RuNO(L)(DMF)Cl3] (L = methyl isonicotinate, 3-cyanopyridine) and cis-(NO, L)-K[RuNO(L)Cl4] (L = ethyl nicotinate) were also confirmed by X-ray analysis.

AB - The mechanism of solvent-assisted ligand substitution in a DMF solution of [RuNOCl5]2- with pyridine-based heterocycles (L) was determined by NMR (15N, 1H) technique. The first substitution stage corresponds to the formation of trans-(NO, DMF)-[RuNOCl4(DMF)]−, which undergoes further substitution with the formation of cis,trans-(NO, L)-[RuNOCl4L]− complexes. The formation of di-substituted products [RuNOCl3L2] depends on the nature of the starting [RuNOCl5]2- salt. For ((C4H9)4N)2[RuNOCl5] the reaction with a 6-7 molar excess of L results mainly in the mixture of cis- andtrans-(NO, L)-[RuNOCl4L]− in the temperature range of 80–140 °C. On the contrary, the reaction of K2[RuNOCl5] with a 6–7 molar excess of L (140 °C, 40–60 min) results mainly in trans-(L, L)-[RuNOCl3L2] (60 %), while other products do not exceed 10–15 % each. The difference was explained by the removal of chloride ions from the DMF solution in the form of KCl. The structure of intermediates and final products in solution was determined based on NMR data. Additionally, some intermediate products with different pyridine-based heterocycles were isolated as individual crystals, and the structures of trans-(NO, DMF)-[RuNO(L)(DMF)Cl3] (L = methyl isonicotinate, 3-cyanopyridine) and cis-(NO, L)-K[RuNO(L)Cl4] (L = ethyl nicotinate) were also confirmed by X-ray analysis.

KW - 1H 15N NMR

KW - Dimethylformamide

KW - N-heterocycle

KW - Nitrosyl

KW - Reaction mechanism

KW - Reaction rate constant

KW - Ruthenium

UR - https://www.scopus.com/pages/publications/105015481636

UR - https://www.mendeley.com/catalogue/96dafc91-c1ac-37be-babd-924b2446947c/

U2 - 10.1016/j.molstruc.2025.143927

DO - 10.1016/j.molstruc.2025.143927

M3 - Article

VL - 1350

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - Part 1

M1 - 143927

ER -