Non-classical polyinterhalides of chlorine monofluoride: Experimental and theoretical characterization of [F(ClF)3]–

We present the synthesis and characterization of the first non-classical Cl(i) polyinterhalide [NMe4][F(ClF)3] as well as the homologous polychloride [NPr3Me][Cl7]. Both salts were obtained from the reaction of the corresponding ammonium chlorides with ClF or Cl2, respectively. Quantum-chemical investigations predict an unexpected planar structure for the [F(ClF)3]- anion.