Electrophilic behaviour of nitrosyls: the reactions of ketones with nitrosyls and the crystal and molecular structure of the product of the reaction between trans-chloro(nitrosyl)tetra(pyridine)ruthenium and acetone

Abstract

The reaction between trans-[RuCl(py)₄(NO)]²⁺(py = pyridine) and acetone in the presence of aqueous NH₃ gave the adduct trans-[RuCl(py)₄{N(O[graphic omitted])CH₃}]⁺, isolated as the PF₆^– salt. The product was characterised by i.r. and n.m.r. spectroscopies and by X-ray diffraction. Crystal data for [RuCl(py)₄{N(O[graphic omitted])CH₃}]PF₆·(CH₃)₂CO are as follows: space group P2₁, a= 8.712(3), b= 14.272(20), c= 13.169(5)Å, β= 104.63(3)°, Z= 2, final R= 0.057 for 268 variables and 1 607 observed reflections. The spectroscopic and diffraction data suggest that the predominant tautomer in the ligand is the delocalised form N([graphic omitted])CH₃. The product decomposed intramolecularly in aqueous solution to give [RuCl(py)₄(NCH)]⁺, which in turn reacted further to give an ill defined paramagnetic complex. In CH₃CN solution, [RuCl(py)₄{N(O[graphic omitted])CH₃}]⁺ decomposed cleanly to give [RuCl(py)₄(NCCH₃)]⁺.