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UBC Theses and Dissertations

Synthetic utilization of the redox properties of some group 6 organometallic nitrosyl complexes Richter-Addo, George Bannerman


The redox behavior of a series of organometallic complexes containing Cp'M(NO) groups (Cp' = ƞ⁵-C₅H₅(Cp) or ƞ⁵-C₅Me₅(Cp*) ; M = Mo or W) has been investigated both by cyclic voltammetry and by chemical means. The neutral 16-electron Cp'Mo(N0)X₂ compounds (X = CL, Br or I) undergo a single, essentially reversible, one-electron reduction in CH₂CL₂/O.1M [n-Bu₄N]PF₆ at relatively low potentials (<-0.1 V vs SCE). The electrochemically observed reductions can be effected on a preparative scale by employing CP₂C0 as the chemical reductant. The isolable 17-electron [Cp'Mo (NO)X₂]•⁻ radical anions are cleanly reconverted to their 16-electron neutral precursors by treatment with [Cp₂Fe]BF₄. In contrast, the Cp'W(NO)I₂ compounds undergo rapid decomposition to their [Cp'W(NO)I]₂ monohalo dimers upon electrochemical reduction. Electrophiles NE⁺ (E = O or ϱ-O₂NC₆H₄N) undergo unprecedented insertions into the Cr-C ϭ-bonds of CpCr(NO)₂R complexes (R = Me, CH₂SiMe₃ or Ph) to afford [CpCr(N0)₂{N(E)R}]⁺ cationic complexes. Present evidence is consistent with these insertions occurring via charge-controlled, intermolecular attacks by NE⁺ at the Cr-R groups in classical SE2 processes. The newly-formed N(E)R ligands function as Lewis bases through nitrogen atoms toward the formally 16-electron [CpCr(NO)₂]⁺ cations and may be displaced from the chromium's coordination sphere by the more strongly coordinating CL⁻ anion. The resulting CpCr(NO)₂CL can be reconverted to CpCr(NO)₂R. thereby completing a cycle by regenerating the initial organometallic reactant. The entire sequence of stoichiometric reactions forming the cycle thus constitutes a selective method for the formation of new carbon-nitrogen bonds, the net organic conversions mediated by the CpCr(NO)₂ group being NE⁺ + R⁻ → N(E)R. The electrophilic [Cp'M(NO)₂]⁺ cations (Cp'=Cp or Cp* ; M = Cr, Mo or W) condense with methyl propiolate and 2,3-dimethyl-2-butene to afford cationic organometallic lactone complexes. These complexes undergo facile ⍜-dealkylation to yield the neutral Cp'M(NO)₂(ƞ¹-lactone) derivatives. Furthermore, the neutral Cp'W(NO)₂(ƞ¹-lactone) compounds decompose in air to their Cp'W(O)₂(ƞ¹-lactone) dioxo products.

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