Thermal deprotonation of coordinated ammine ligands

In an early study of the solid state thermal deprotonation of coordinated ammine ligands, Tsin-Shen and Tronev S showed that ReCl3 4NH3 (a compound of uncertain structure) was transformed into a diamido-complex by loss of HCl, Eq. 12.16  

The same diamido-complex was prepared by treatment of ReCl3-4NH3 with liquid ammonia. Further heating of [ReCl(NH2)2(NH3)2] resulted in the formation of the imido-complex, [Re2(NH)Cl]n, and, ultimately, rhenium nitride, [Re2N]n-  

In a similar fashion, heating [ReCl4(NH3)] in the solid state results in a conversion of a coordinated ammine ligand into an amide and, then, into a nitride, Eqs. 12.17-12.18  

A related rhenium nitride compound, [ReFN], has been produced through the thermal decomposition of [NH4]2[ReF6] at 300 under argon, Eq. 12.19  

The first stage in this process is likely to be an Anderson rearrangement, followed by deprotonation of the coordinated ammine. The complex [NH4]2[TcF5l has been shownSO to be subject to a similar transformation. 

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