Synthesis and Crystal Structure of a Cationic Oxo-Bridged Nitridoruthenium(VI) Complex with a Chelating Diamine Ligand Having No α-CH Group

Abstract

[(n-Bu)4N][RuNCl4] reacts with 2,5-dimethyl-2,5-hexanediamine (L) in acetone to give a cationic dimeric RuVI⋮N complex [(RuVI(L)2N)2(μ-O)]Cl4 (1). The X-ray crystal structure of 1·H2O has been determined. The structure of 1 shows two Ru⋮N units bridged by a μ-oxo ligand. The Ru⋮N and Ru−O bond distances are 1.66(1) and 1.9896(8) Å, respectively.

Vicinal Dinitridoruthenium‐Substituted Polyoxometalates γ‐[XW10O38{RuN}2]6− (X=Si or Ge)

“…Previously, [78] we arrived at the same conclusion for polyoxometalates g-[XW 10 O 36 ] (n-4)À with X = P 5 + , Si 4 + , Al 3 + , and S 6 + , that is, X from the same-row elements. The ruthenium-nitrido bond length is almost identical in both species (1.594(10) in 1 a, 1.612(11) in 1 b), and falls well within the relatively narrow range of values reported for Ru VI ÀN (from 1.57 [79] to 1.62 , [80] except for two complexes at 1.66 [32,39] With structures so similar, it is more than likely that the reactivities of 1 a and 1 b are identical. Therefore, the study presented here concentrates mainly on the silicon derivative 1 a.…”

“…Two bands attributed to the DMA cation are the only signals observed between 1000 and 1100 cm À1 , the region where the (usually weak) Ru N stretching vibration is most likely to be found. [32,51] This mode, however, is Raman active and indicated by a strong band at 1080 cm À1 (Figure 4).…”

“…[30][31][32][33][34][35] The versatility of the ruthenium-nitrido function, sometimes electrophilic, [15,[36][37][38] sometimes nucleophilic, [39] prompted us to chose this metal for our investigations.The ligands we used are the divacant silicotungstate g-[SiW 10 O 36 ] 8À and its germanium analogue g-[GeW 10 O 36 ] 8À . In contrast to the ruthenium complexes with diamine, [32] or multianionic chelating (N, O) ligands, [37] and Shapleys alkyl complexes, [33][34][35] where the assembly of the two ruthenium centers takes place somewhat haphazardly, the rigidity of the polyoxometalate framework should facilitate good control of the relative geometry of the metal-nitrido functional groups. We thus report herein the synthesis of the binuclear derivatives g-[XW 10 O 38 A C H T U N G T R E N N U N G {RuN} 2 ] 6À (X = Si (1 a) or Ge (1 b)), characterization of their geometric and electronic structures, and formation of ammonium by reduction of 1 a.…”

“…However, multi-nitrido derivatives to date are quite rare. [30][31][32][33][34][35] The versatility of the ruthenium-nitrido function, sometimes electrophilic, [15,[36][37][38] sometimes nucleophilic, [39] prompted us to chose this metal for our investigations.…”

Ruthenium Nitrides: Redox Chemistry and Photolability of the Ru-Nitrido Group

“…To this end we considered the ruthenium ion in meso ‐octamethylporphyrinogen,6 which is related to porphyrin—the macrocycle par excellence in ruthenium chemistry. Ruthenium nitride chemistry7 has received considerable attention in the recent past, and some major issues are considered here: 1) the formation of the Ru≡N group by cleavage of N−N bonds7 which mimic the N 2 molecule; 2) the redox chemistry associated with the [Ru≡N] fragment, with the intent of tuning the nucleophilic–electrophilic properties of the nitrido group;7a,7b 3) the relationship between the terminal [Ru≡N] and the bridging [Ru=N=Ru] groups; 4) the photolabilization of Ru−N bonds; and 5) the use of a tetrapyrrolic macrocycle related to porphyrin, a key ligand in Ru chemistry and one with which the Ru≡N group has so far not been associated.…”