350832-46-1Relevant articles and documents
A family of organoruthenium nitrites: Alkyne insertion, linkage isomerization and ring nitration
Chattopadhyay,Ghosh,Pattanayak,Chakravorty
, p. 1259 - 1265 (2001)
The reaction of [Ru(C6H2OH-2-CHNR-3-Me-5) (PPh3)2(CO)(NO2)] 1 (R = Et, p-MeC6H4 or p-ClC6H4) with an excess of alkyne HC≡CX (X = H, Ph or CH2OH) in CH2Cl2-MeOH medium was accompanied by linkage isomerization of nitrite (O,O′-bonded → N-bonded) and formation of a six-membered vinyl-phenolato chelate ring to give [Ru(η2-C6H2CXCH-1-O-2-CHNHR-3-Me-5) (PPh3)2(CO)(NO2)] 4. The active substrate is the solvate 1·MeOH, and the 2 + 2 addition of the bulky ≡CX (X = Ph or CH2OH) group proceeds regiospecifically to the carbon end of the Ru-C bond. Compound 4 has also been obtained metathetically by treating 3 (the chloro analogue of 4) with NaNO2 in neutral media. However in acid media ring nitration of 3 (R = Et, X = Ph) occurs furnishing [Ruη2-C6HCPhCH-1-O-2-CHNHEt-3-NO2-4- Me-5)(PPh3)2(CO)Cl] 7 which can metathetically be converted into the corresponding N-bonded NO2 analogue, 8. The iminium proton is hydrogen bonded to the phenolato oxygen in 4, 7 and 8 and also weakly to a nitro oxygen in 4 and 8 (IR and 1H NMR data). All the species display a quasireversible cyclic voltammetric RuIII-RuII couple, the E1/2 of which shifts to higher potential by ≈200 mV upon replacing chloride by nitrite (3 → 4; 7 → 8) as well as upon aromatic nitration (3 → 7). The crystal structures of the solvate 4b·C6H6 in which R = p-MeC6H4 and X = H, 4h in which R = p-ClC6H4 and X = CH2OH and 7 have been determined. The σ-vinyl-phenolato chelate ring is approximately planar. The Ru-N bond in the planar RuNO2 fragment of 4b·C6H6 and 4h is lengthened by ≈0.1 A due to the trans influence of the vinyl group. The Ru-C(vinyl) bond in 7 is significantly shortened due to electron withdrawal by the nitro group, thus promoting Ru-ligand back bonding. The distances of the iminium nitrogen from phenolic oxygen and a nitrito oxygen (in 4b·C6H6 and 4h) lie in the ranges 2.55-2.67 and 2.90-2.98 A respectively.