The reactions of TiCl₃, and of UF₄with TiCl₃in liquid ammonia: unusual coordination spheres in [Ti(NH₃)₈]Cl₃·6NH₃and [UF(NH₃)₈]Cl₃·3.5NH₃

Abstract

TiCl3 and NH3 form octaammine titanium(III) chloride ammonia (1/6), [Ti(NH3)8]Cl3·6NH3, which is the first structurally characterized octaammine complex of a transition metal. An excess of TiCl3 reacts with UF4 in liquid NH3 and forms octaammine fluorido uranium(IV) chloride ammonia (1/3.5), [UF(NH3)8]Cl3·3.5NH3. It shows a distorted threefold-capped trigonal-prismatic coordination sphere around U(IV).

Reactions of ThX4 (X=F, Cl, Br, I) with Liquid Ammonia‐Crystal Structures and a Theoretical Study of Ammine Thorium(IV) Halide Ammoniates

“…These hydrogen bonds for the different decaammine thorium(IV) halides are in good agreement with known N−H⋅⋅⋅ X ( X= Cl, Br, I) hydrogen bonds for example in [Co(NH 3 ) 6 ]Cl 2 (3.601 Å, T =294 K), [Co(NH 3 ) 6 ]Br(S 2 O 3 ) ⋅ H 2 O (3.509(4) to 3.539(3) Å, T =295 K) or [CoCO 3 (NH 3 ) 5 ]Br ⋅ H 2 O (3.41 to 3.63 Å), or [Co(NH 3 ) 6 ]I 3 (3.902 Å, T =298 K) [10,31‐36] …”

Uranium Chemistry in liquid Ammonia: Compounds obtained by adventitious Presence of Moisture or Air

“…This motif has frequently been observed for UO 2 2 + compounds obtained from aNH 3 . [9,15,16,45] The coordination polyhedra are corner-connected via the μ-O 2À ligand. All U�O bond lengths are equal within their tripled standard uncertainties in a range from 1.793(3) to 1.811(3) Å.…”

Laser-Induced Thermal Decomposition of Uranium Coordination Compounds with Non-oxidic Ligands to Produce Nitride and Carbide Materials

“…The premise behind studying actinide coordination compounds was first to study novel structures and reactivities, − as well as understanding their bonding properties . Uranium can adopt high coordination numbers and a wide range of oxidation states. − A multitude of coordination environments, − more specifically halides , (the gateway to synthetic actinide chemistry), can be synthesized and studied to grow the coordination chemistry knowledge of what is still a relatively young field in producing these compounds with actinides. ,,− The study of converting uranium coordination compounds to uranium ceramics can be achieved through thermal processing. Under laser irradiation, the combination of the rapid heating (up to 2600 °C in less than 1 ms , ) and the fast cooling rates (10 6 K/s , ) allows for reaction environments and kinetics rarely achieved via conventional methods .…”