Electrophilic behaviour of nitrosyls: the Boedeker reaction, the reactions of sulphite with nitrosyls, and the crystal and molecular structure of cis-bis(2,2′-bipyridine)chloro(nitrosylsulphito)ruthenium
Abstract
Similar adducts to that, [Fe(CN)5{(NO)(SO3)}]4–, formed in the Boedeker reaction have been obtained by the reaction of SO32– with trans-[RuCl(py)4(NO)]2+(py = pyridine) or cis-[RuX(bipy)2(NO)]2+(X = Cl or Br, bipy = 2,2′-bipyridine). These adducts, [RuCl(py)4{N(O)SO3}] and cis-[RuX(bipy)2{N(O)SO3}], are shown, principally by i.r. spectroscopy, to contain identical [N(O)SO3]– ligands to [Fe(CN)5{N(O)SO3}]4–. The structure of cis-[RuCl(bipy)2{N(O)SO3}] has been determined by X-ray diffraction. It is best regarded as a ruthenium(II) complex containing the hitherto unknown ligand [ONSO3]– which is N-co-ordinated to RuII. The ligand has a long (1.82 Å) and weak (force constant 137 N m–1) N–S bond. The reversibility of the adduct formation is demonstrated. Crystal data for cis-[RuCl(bipy)2{N(O)SO3}]: orthorhombic, space group Pbca, a= 14.48(2), b= 19.49(2), c= 14.49(1)Å, final R= 0.063 for 290 variables and 1 370 observed reflections. The ruthenium is in a distorted octahedral environment.
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