New features in the redox coordination chemistry of metal nitrosyls {M–NO+; M–NO; M–NO−(HNO)}

On the Electronic Structure ofmer,trans‐[RuCl3(1H‐indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

“…[25,29] The (nonmeasurable) formal configuration of {Ru II -(NO) + } 6 is physically better described as {Ru III (NO 0 )} 6 , which provides another example of the discrepancy between formal and physical oxidation states in metal complexes. [23,28,34] …”

“…[24,26] However, there are two possible resonance structures available for interpreting the electron configuration of the {Ru(NO)} 6 entity. The first is the {Ru II (NO + )} 6 system [24,26,28,34] with strong π backdonation of the electron density from ruthenium to the NO ligand, which accounts for 1.06 electrons (when considering the Mulliken populations of the localized orbitals). The second resonance structure {Ru III (NO 0 )} 6 implies two closely degenerate π bonds between Ru and N3, although stabiliza- Figure 8 and have almost the same shapes and Mulliken populations as found for 2 and 3.…”

“…[78] Compounds 1 and 3 in the singlet spin state (closed shell) as well as compounds 2 and 3 + (the one-electron oxidized compound 3) in the doublet spin state (open shell) were investigated. The LANL (28) [79] effective core potential and LANL08 [80] basis set were used for the Ru atom, and the remaining atoms were treated by using the cc-pVDZ basis sets [81,82] (abbreviated as ECP-DZ). The presented frontier orbitals and localized or-bitals (using the Pipek-Mezey procedure) were obtained by using the same ECP-DZ basis sets.…”

“…However, this notation leaves the actual physical and formal oxidation state [23] of the metal center and nitrosyl ligand unclear, and therefore it remains a subject of notable interest. [24][25][26][27][28][29][30][31][32][33][34][35][36][37] This study is an attempt to describe such a {Ru(NO)} 6 -containing system in more detail.…”

Chromatographic Investigation of Ruthenium Nitrosyl Complex: No Interconversion and Reactions With Biological Reductants

“…Some reactions of nucleophiles with nitrosyl complexes have been reviewed, [36][37][38][39][40] leading to the formation of gas (N 2 or N 2 O) as result of the adduct decompositions. Intermediate adducts have showed strong absorption around 520 nm as noticed during a fast reactions of nitroprusside and diverse thiolates, [41][42][43] leading to the reduction of nitric oxide and the oxidation of the thiolates.…”