Unexpected lability of the [Ru^III(phtpy)Cl₃] complex

Abstract

Ruthenium(iii) complexes are known for their high stability and inertness. To the best of our knowledge, the only well-characterized example of a labile Ru(iii) complex is [Ru(edta)(HO)] as a consequence of an intramolecular hydrogen bonding leading to the formation of a large opening in the molecule front, thus changing the mechanism from dissociative to associative. Compelling experimental evidence is presented demonstrating that the [Ru(phtpy)Cl] complex is labile, also indicating that the Ru(iii)-phtpy bond is much weaker than expected, in contrast to the strongly π-back-bonding stabilized Ru(ii)-phtpy bond.

Ruthenium Azobis(benzothiazole): Electronic Structure and Impact of Substituents on the Electrocatalytic Single-Site Water Oxidation Process

“…The partially overlapping aromatic resonances due to their similar chemical shift values were further analyzed by 2D-NMR ( 1 H- 1 H COSY and NOESY) (Figures S3–S6 in the Supporting Information). It is worth noting that the equivalent C21 and C29 protons of 4′-Ph-trpy (Figure and Figures S3–S6 in the Supporting Information) in each case were resolved as a singlet at δ ≈ 9.20 ppm. , …”

“…The precursor complex [Ru III (Ph-trpy)­Cl 3 ] , and ligands (L1–L3) were prepared according to the procedures reported in the literature. Other chemicals and solvents were of reagent grade and were used as received.…”

Identification of a chemical fingerprint linking the undeclared 2017 release of 106 Ru to advanced nuclear fuel reprocessing

“…In particular, we have identified the subsequent monoligated complex, ttpyRuCl 3 ( 37 ), and the reduced, bis-ligated complex, Ru(ttpy) 2 2+ ( 38 ), as targeted reaction products for isolation and radiometric measurement, in adherence to the general strategy presented in Scheme 1 . Although the former has invariably served as a reaction intermediate to the formation of heteroleptic complexes ( 39 , 40 ), it takes center stage in this work. This is due to the fact that the formation of ttpyRuCl 3 (or related complexes based upon 2,2′:6′,2″-terpyridine) is expected to be highly selective to β-RuCl 3 and related compounds, considering that there is no alteration in oxidation state or local coordination geometry about the ruthenium atom.…”

“…While the formation of ttpyRuCl 3 has only ever been performed from β-RuCl 3 ( 37 , 40 ), we undoubtedly expect the reaction to proceed to an appreciable extent from higher-order polychlorinated Ru(III) compounds, given the favorable binding interaction afforded by the tridentate ligand, ttpy, and considering that their solution equilibria in dative solvent will include the formation of RuCl 3 ( 41 , 42 ). Nevertheless, by defining the applicable scope of this reaction, we refine and gain confidence in the types of contaminant ruthenium species that could lead to the observed formation of ttpy 106 RuCl 3 .…”

Platinum(terpyridine) complexes with N-heterocyclic carbene co-ligands: high antiproliferative activity and low toxicityin vivo

“…Interestingly, we found evidence that the ether linking the mustard and the tpy were cleaved upon coordination to the Pt centre, which led us to investigate this observation further. We prepared the terpyridine ligands 2,6-bis(2-pyridyl)-4[1 H ]-pyridone ( a ), 24 and 4′-phenyl-2,2′:6′,2′′-terpyridine ( b ) 25 (compare Scheme 1 for the structures) following literature methods. To facilitate the formation of the Pt(NHC) complexes of these tpy ligands, precursor 1 was obtained by reacting cis -[PtCl 2 (DMSO) 2 ] 26 with 1,3-dimethylbenzimidazolium hexafluorophosphate in the presence of NaHCO 3 .…”