Phosphinimine complexes of technetium(VII): X-ray crystal structure of [Ph3P=NH+2][TcO4]1

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An X-ray diffraction study and the solution chemistry is reported for the very stable ion pair [Ph3P=NH+2][TcO4]. This compound crystallizes in the orthorhombic system, in space group P212121, with cell dimensions of a = 11.1454(6), b = 11.449(2), and c = 14.570(2)Å, and refining to R = 0.023 and RW = 0.031. Strong hydrogen bonds are formed between the iminium protons and the pertechnetate oxygens (1.89(6) and 2.23(6) Å) in the solid state, and similar hydrogen bonding apparently occurs in aqueous solution to stabilize the phosphiniminium cation to hydrolysis.

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