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Heterocumulene insertions with group 6 Diaryl Nitrosyl complexes Brouwer, Eric B.


Treatment of the 16-electron complexes Cp*M(NO)(aryl)2 (Cp* = i5-05Me5; M =Mo, W; aryl = phenyl, o-tolyl, p-tolyl) with the heterocumulenes carbon dioxide, p-tolylisocyanate, and carbon disulfide leads to the i2-carboxylate-, i2-amide-, and i2-thiocarboxylate-containing complexes, respectively, in 10-50% yields. Treatment with a fourth member of the heterocumulene class, diphenylketene, does not result in an isolable inserted complex, although spectroscopic data suggest that insertion has taken place. Cp*M(NO)(aryl)2 complexes thus insert one heterocumulene molecule into a metal-aryl bond; the other metal-aryl bond is inert to further insertion. The resulting complexes are thermally stable and air-stable, and can be described as being 18-electron species. Protonolysis of the representative heterocumulene-inserted complex Cp*W(NO){112-N(p-tol)C(0)Ph}Ph releases the functionalized heterocumulene molecule, p-tolylbenzamide.All new complexes have been fully characterized by conventional methods. In addition, Cp*W(NO)(r12-S2CPh)Ph reacts with the Lewis base trimethylphosphine to form Cp*W(NO){112-S2C(PMe3)Ph}Ph which contains a zwitterionic phosphonium-betaine ligand. X-ray crystallographic studies of Cp*W(NO){1.12-82C(PMe3)Ph}Ph and Cp*W(N0)(112-0NPh)(NPh)Ph are reported and discussed.

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