Ammonia Uptake and Release in the MnX2–NH3 (X = Cl, Br) Systems and Structure of the Mn(NH3)nX2 (n = 6, 2) Ammines

doi:10.3390/cryst2020193

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Crystals 2012, 2(2), 193-212; doi:10.3390/cryst2020193

Article

Ammonia Uptake and Release in the MnX₂–NH₃ (X = Cl, Br) Systems and Structure of the Mn(NH₃)_nX₂ (n = 6, 2) Ammines

Hazel Reardon, James M. Hanlon, Michael Grant, Imogen Fullbrook and Duncan H. Gregory*

WestCHEM, School of Chemistry, University of Glasgow, Joseph Black Building, Glasgow G12 8QQ, UK

* Author to whom correspondence should be addressed.

Received: 21 February 2012; in revised form: 18 March 2012 / Accepted: 30 March 2012 / Published: 10 April 2012

(This article belongs to the Special Issue Hydrogen Storage Alloys)

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Abstract: Hexa-ammine complexes, Mn(NH₃)₆X₂ (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(NH₃)₆X₂ complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH₃ 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: orthorhombic Cmmm, 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).

Keywords: manganese; ammines; chloride; bromide; structure; Raman; ammonia storage; hydrogen storage

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Cite This Article

MDPI and ACS Style

Reardon, H.; Hanlon, J.M.; Grant, M.; Fullbrook, I.; Gregory, D.H. Ammonia Uptake and Release in the MnX₂–NH₃ (X = Cl, Br) Systems and Structure of the Mn(NH₃)_nX₂ (n = 6, 2) Ammines. Crystals 2012, 2, 193-212.

AMA Style

Reardon H, Hanlon JM, Grant M, Fullbrook I, Gregory DH. Ammonia Uptake and Release in the MnX₂–NH₃ (X = Cl, Br) Systems and Structure of the Mn(NH₃)_nX₂ (n = 6, 2) Ammines. Crystals. 2012; 2(2):193-212.

Chicago/Turabian Style

Reardon, Hazel; Hanlon, James M.; Grant, Michael; Fullbrook, Imogen; Gregory, Duncan H. 2012. "Ammonia Uptake and Release in the MnX₂–NH₃ (X = Cl, Br) Systems and Structure of the Mn(NH₃)_nX₂ (n = 6, 2) Ammines." Crystals 2, no. 2: 193-212.

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