SYNTHESIS, CHARACTERIZATION AND REACTIONS OF TERTIARY PHOSPHINE COMPLEXES OF COBALT DERIVATIVES OF NITROGEN OXIDES.
AdvisorFeltham, Robert D.
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PublisherThe University of Arizona.
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AbstractCo(NO)(NO₂)₂L₂ complexes (L = PPh₃, PMePh₂, PMe₂Ph, PMe₃, PEt₃, PEt₂Ph, PEtPh₂, PPrPh₂, PBu₃ and 1/2DPPPr) were prepared from the reactions of Co(NO)X₂L₂ (X = Cl, Br) with sodium nitrite in methanol freshly distilled from magnesium methoxide. The complexes were characterized by elemental analysis, 15-N labeling, infrared and NMR spectroscopy. The crystal structure of Co(NO)(NO₂)₂(PMePh₂)₂ was determined by X-ray diffraction. The cobalt atom has tetragonal pyramidal geometry. The nitrosyl group in the axial position is strongly bent. The NO₂ ligands have two different ligating geometries: one is bound to cobalt through the nitrogen atom and the other is bidentate forming an asymmetric four membered ring. The phosphine ligands are equivalent and trans to each other. Multinuclear NMR spectroscopy (¹H, ³¹P, ¹⁵N and ¹⁴N) was used to determine the solution structure of Co(NO)(NO₂ )₂L₂ complexes, to study mono and bisnitrosyls of cobalt, to establish some correlations between NMR parameters and structural characteristics of these complexes and to follow their reactions in solution. Reactions of Co(NO)(NO₂)₂L₂ with CO, NO and RCOX were observed to produce Co(NO)₂XL complexes. Since the structure may be indicative of electronic requirements at the metal center as well as the reactivity of the compounds, The crystal structures of Co(NO)₂Cl(PPh₃) and Co(NO)₂(ONO)(PPh₃) were also determined. In these complexes the cobalt atoms have pseudotetrahedral geometry. The CoNO angles are in the range considered to be linear. They are geniculated in an "atracto" conformation. Co(NO)(NO₂)₂L₂ and Co(NO)₂(ONO)L complexes react with oxygen in the solid state or in solution to form Co(NO₃)₂(OL)₂ complexes. When the reactions with O₂ were carried out in the presence of an excess of olefins, the formation of nitrates is inhibited Co(NO₂)₂(OL)₂ and olefin oxides are formed instead. The crystal structures of Co(NO₃)₂(OPMePh₂)₂ and Co(NO₂)₂(OPMePh₂)₂ were determined by X-ray diffraction. In these complexes, the NO₃ and NO₂ groups are bidentate. They are arranged in a cis configuration around the cobalt atom.