Ammonia uptake and release in the MnX₂–NH₃ (X = Cl, Br) systems and structure of the Mn(NH₃)nX₂ (n = 6, 2) ammines

Abstract

Hexa-ammine complexes, Mn(NH<sub>3</sub>)<sub>6</sub>X<sub>2</sub> (X = Cl, Br), have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD) and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic,Fm-3m, Z = 4; a = 10.2742(6) Å and 10.527(1) Å for X = Cl, Br respectively). Temperature programmed desorption (TPD) demonstrated that ammonia release from Mn(NH<sub>3</sub>)<sub>6</sub>X<sub>2</sub> complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH<sub>3</sub> equivalents respectively. The chloride and bromide both exhibit a deammoniation onset temperature below 323 K. The di-ammoniates from the first desorption step were isolated during TPD measurements and their crystal structures determined by Rietveld refinement against PXRD data (X = Cl: orthorhombicCmmm, a = 8.1991(9) Å, b = 8.2498(7) Å, c = 3.8212(4) Å, Z = 2; X = Br: orthorhombic Pbam, a = 6.0109(5) Å, b = 12.022(1) Å, c = 4.0230(2) Å, Z= 2)