Reactions of [MCl6]2− (M=Tc or Re) with salicylaldehyde. The molecular structure of tetraphenylphosphonium tetrachloro(salicylaldehydato) technetate (IV)

Summary The [PPh₄][TcCl₄(sal)] and [PPh₄][ReOCl₃(sal)] (sal=o-OC₆H₄CHO) complexes were synthesized from [PPh₄]₂[MCl₆] (M=Tc or Re) and salicylaldehyde. The complexes were characterized by elemental analysis, magnetic susceptibility and conductivity measurements and i.r. spectrometry. The structure of [PPh₄][TcCl₄(sal)] was determined by x-ray methods and consists of well-separated units of octahedral [TcCl₄(sal)]^– anions and tetrahedral [PPh₄]⁺ cations. The equatorial plane of the octahedron is formed by two Cl atoms and the chelated(2) sal group, with the resulting TcCl₂(sal) unit approximately planar. Selected values in the anion are as follows: Tc-Cl(mean) 2.34(1), Tc-O(1) 2.04(2) and Tc-O(2) 1.98(2), O(1)---O(2)(byte) 2.83 Å; O(1)-Tc-O(2) 89.3(0.7)^o.