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

Abstract
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 [MN{ButNC(O)NBut}Cl2], M = Ru or Os. X-Ray diffraction studies have shown the anions to have distorted square-pyramidal geometry with 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 Me2CCH2 and HCl. Similar reactions using other aryl and alkyl isocyanates gave intractable products. The compound W[ButNC(O)NBut]2(NHBut)2 is formed on reaction of W(NBut)2(NHBut)2 with ButNCO.

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