Notes. Synthesis and crystal structures of [PPh4][MN{ButNC(O)NBut}Cl2](M = Ru or Os); a new reaction of tert-butyl isocyanate. Synthesis of W[ButNC(O)NBut]2(NHBut)2
作者:Wa-Hung Leung、Geoffrey Wilkinson、Bilquis Hussain-Bates、Michael B. Hursthouse
DOI:10.1039/dt9910002791
日期:——
The interaction of the tetraphenylphosphonium salts of the ruthenium- and osmium-(VI) anions [RuO2Cl3]-, [RuO2Cl4]2- and [OsO2Cl4]2- with excess of tert-butyl isocyanate in acetonitrile forms the salts of the anions [MNBu(t)NC(O)NBu(t)}Cl2]-, M = Ru or Os. X-Ray diffraction studies have shown the anions to have distorted square-pyramidal geometry with the nitrido groups in axial positions. The metal nitrido groups have been shown to arise by C-N bond cleavage of unisolated tert-butylimido intermediates accompanied by cycloelimination of Me2C = CH2 and HCl. Similar reactions using other aryl and alkyl isocyanates gave intractable products. The compound W[Bu(t)NC(O)NBu(t)]2-(NHBu(t))2 is formed on reaction of W(NBu(t))2(NHBu(t))2 with Bu(t)NCO.