A series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)₂X(L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH₃O (2b)) and [OsVI(N)(L)X₃]⁻ (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)₂X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh₃)(L)₂X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)₂Br (2c) (L =2-quinaldinate) with triphenylphosphine have been studied in CH₃CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained:-d[Os(VI)]/dt = k₂[Os(VI)][PPh₃]. OsVI(N)(L)₂Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N₃) to give an osmium(III) dichloro complex, trans-[PPN][Osˡˡˡ(L)₂Cl₂] (6). Reaction of OsVI(N)(L)₂Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex Osˡˡ(NS)(L)₂Cl (7). These complexes have been structurally characterised by X-ray crystallography. Copyright © 2009 Elsevier B.V. All rights reserved.
CitationLeung, C.-F., Yiu, D. T. Y., Wong, W.-T., Peng, S.-M., & Lau, T.-C. (2009). Synthesis and reactivity of osmium (VI) nitrido complexes containing pyridine-carboxylato ligands. Inorganica Chimica Acta, 362(10), 3576-3582. doi: 10.1016/j.ica.2009.04.002
- Osmium(VI) nitride