Behavior of nitrite forms of nitrosylruthenium on extraction and back extraction of heterometalic Ru/Zn complexes with trioctylphosphine oxide

Reaction of [RuNO(NO2)4OH]2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes

“…For both complexes, the positions of the NO 2 signals correspond to O 2 N –Ru–O coordination. [11a] The data for complex B corresponds well to those reported in ref. [11a] and can be assigned to [RuNO(H 2 O) 3 (NO 2 ) 2 ].…”

“…[11a] The data for complex B corresponds well to those reported in ref. [11a] and can be assigned to [RuNO(H 2 O) 3 (NO 2 ) 2 ]. Complex A should be assigned to unsymmetrical [RuNO(NO 2 ) 2 (H 2 O) 2 (SO 4 )], in which the sulfate ion (or hydrosulfate) is coordinated through one oxygen atom.…”

“…To clarify these results and to determine the intermediate products we performed a 15 N NMR spectroscopic study. The resonances in the NMR spectra were assigned by taking into account the following points: 1) The relationship between integral intensities, 2) the different groups manly show signals in three regions, namely 200–230 (ONO k ), 60–100 (NO 2k ), and –50–0 ppm (NO k ),[7b], 3) the strong dependence of the chemical shifts on the nature of the trans partner, and 4) the possible chemical transformations in the investigated solutions. The relative amounts of the different complexes were evaluated from the ratio of the integral intensities corresponding to NO k .…”

“…The spectrum of the final mixture exhibits two broad (1000–2000 Hz) signals at δ = 75 ppm (corresponding to NO 2 ) and –19 ppm (corresponding to NO) with relative intensities of 2:1. In a recent paper[11a] describing the interaction of An 2– with nitric acid, 15 N NMR signals at 60.4 (NO 2 ) and –23.6 ppm (NO) were attributed to OC‐6‐34‐[RuNO(H 2 O) 3 (NO 2 ) 2 ] . Taking into account the difference in solution composition and line‐broadening in the 14 N NMR spectra, these data can be considered similar.…”

“…The upfield shift for the signal of this nitrogen atom trans to water compared with the nitrogen atom trans to pyridine correlates with the trans influence of the ligands and is typical of such complexes. [11a], The 15 N NMR spectrum of solution IV, prepared after the addition of pyridine directly to solution I without the precipitation of SO 4 2– , contains two sets of signals corresponding to the two dominant forms C and D (Table ) present in relative proportions of 28 and 72 %. The positions of the signals corresponding to complex C ([RuNO(NO 2 ) 2 (H 2 O) 2 Py]) in spectrum IV are very close to those in spectrum III ( δ = 85.2 ppm for O 2 N –Ru–Py, 81.4 ppm for O 2 N –Ru–H 2 O, and –35.3 ppm for O N –Ru–OH).…”