Synthesis, Crystal Structure, and IR Investigations of [(NH₃)₅VOV(NH₃)₅]I₄ · NH₃ and [(NH₃)₅TiOTi(NH₃)₅]I₄ · NH₃

Abstract

Abstract The reaction of VI 2 or TiI 3 , respectively, with ammonia in the presence of traces of water or oxygen, respectively, leads to [(NH 3 ) 5 MOM(NH 3 ) 5 ]I 4 · NH 3 with M = V, Ti. Their structures were solved by X‐ray single crystal data: Pbca (No. 61), Z = 4, M = V: a = 12.482(4) Å, b = 14.819(6) Å, c = 13.286(5) Å, N(F ⩽ 3σF ) = 983, N(variables) = 88, R/R w = 0.053/0.063, M = Ti: a = 12.628(4) Å, b = 14.970(4) Å, c = 13.359(3) Å, N(F ⩽ 3σF ) = 1188, N(variables) = 88, R/R w = 0.043/0.047. The structures consist of corner sharing octahedra double units [(NH 3 ) 5 MOM(NH 3 ) 5 ] 4+ with eclipsed conformation which are stacked together according to the motif of a distorted cubic face centered arrangement for the bridging oxygen atoms. IR spectroscopic investigations of the undeuterated vanadium compound and of 5% deuterated samples hint to NH … I hydrogen bridge bonds and to remarkable π‐bonding between the transition metal and the bridging oxygen atoms.