Synthesis of Nitrosylruthenium Complexes Containing 2,2‘:6‘,2‘ ‘-Terpyridine by Reactions of Alkoxo Complexes with Acids

Abstract

Nitrosylruthenium complexes containing 2,2':6',2"-terpyridine (terpy) have been synthesized and characterized. The three alkoxo complexes trans-(NO, OCH3), cis-(Cl, OCH3)-[RuCl(OCH3)(NO)(terpy)]PF6 ([2]PF6), trans-(NO, OC2H5), cis-(Cl, OC2H5)-[RuCl(OC2H5)(NO)(terpy)]PF6 ([3]PF6), and [RuCl(OC3H7)(NO)(terpy)]PF6 ([4]PF6) were synthesized by reactions of trans-(Cl, Cl), cis-(NO, Cl)-[RuCl2(NO)(terpy)]PF6 ([1]PF6) with NaOCH3 in CH3OH, C2H5OH, and C3H7OH, respectively. Reactions of [3]PF6 with an acid such as hydrochloric acid and trifluoromethansulforic acid afford nitrosyl complexes in which the alkoxo ligand is substituted. The geometrical isomer of [1]PF6, trans-(NO, Cl), cis-(Cl, Cl)-[RuCl2(NO)(terpy)]PF6 ([5]PF6), was obtained by the reaction of [3]PF6 in a hydrochloric acid solution. Reaction of [3]PF6 with trifluoromethansulforic acid in CH3CN gave trans-(NO, Cl), cis-(CH3CN, Cl)-[RuCl(CH3CN)(NO)(terpy)]2+ ([6]2+) under refluxing conditions. The structures of [3]PF6, [4]PF6.CH3CN, [5]CF3SO3, and [6](PF6)2 were determined by X-ray crystallograpy.

Ruthenium Nitrosyls Derived from Tetradentate Ligands Containing Carboxamido-N and Phenolato-O Donors: Syntheses, Structures, Photolability, and Time Dependent Density Functional Theory Studies

“…In 1 , the bound NO molecule is trans to the EtO − ligand and the Ru-NO distance (1.735 Å) as well as the Ru-NO bond angle (170.5°) are as expected for this type of {Ru-NO}6 nitrosyls. Finally, the Ru-OEt bond distance (1.975 Å) of 1 is longer than that observed for other ruthenium nitrosyls containing an EtO − ligand trans to NO, such as trans -[Ru(OEt)(2mqn) 2 NO] (1.928 Å)36 and trans -(NO, OC 2 H 5 ), cis -(Cl, OC 2 H 5 )-[RuCl-(OC 2 H 5 )(NO)(terpy)]PF 6 (1.943 Å) 37…”

Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

“…However, it is important to bear in mind that great care must be taken in the analysis of the shifts in energy observed for ν(NO) in the solid state. For instance, it has been reported that ruthenium-nitrosyl complexes containing terpyridine could exhibit ν(NO) bands at different frequencies, depending on the nature of the counter ion (e.g., with PF 6 - [28] and Cl - [29] ), due to different solid-state environments. Nevertheless, the data obtained from DFT computations performed on isolated cationic complexes confirm the tendency (Table 4).…”

Comparative photo-release of nitric oxide from isomers of substituted terpyridinenitrosylruthenium(ii) complexes: experimental and computational investigations

“…32 The synthesis of the [Ru II (FT)Cl 2 (NO)](PF 6 ) derivatives was carried out by following a procedure previously reported by Nagao et al using unsubstituted terpyridine. 33 In fact, when K 2 [RuCl 5 (NO)] reacts with terpyridine, the authors stated that the trans(Cl,Cl)-[Ru II (terpy)Cl 2 (NO)](PF 6 ) isomer is obtained exclusively (yield 54%) whereas the use of [RuCl 3 (H 2 O) 2 (NO)] leads to the cis(Cl,Cl)-derivative (yield 44%) according to Reedijk. 34 In the present investigation, the 1 33 as we have recently observed in analogous ruthenium complexes.…”

“…33 In fact, when K 2 [RuCl 5 (NO)] reacts with terpyridine, the authors stated that the trans(Cl,Cl)-[Ru II (terpy)Cl 2 (NO)](PF 6 ) isomer is obtained exclusively (yield 54%) whereas the use of [RuCl 3 (H 2 O) 2 (NO)] leads to the cis(Cl,Cl)-derivative (yield 44%) according to Reedijk. 34 In the present investigation, the 1 33 as we have recently observed in analogous ruthenium complexes. 35 The chemical shifts of all the signals were identified from two dimensional NMR HMBC, HSQC, long and short range COSY spectra for cis-and trans-complexes.…”