
Journal of the American Chemical Society p. 7945 - 7952 (1985)
Update date:2022-07-29
Topics:
Osborne, Joseph H.
Rheingold, Arnold L.
Trogler, William C.
The reaction between Cp*2V a = 8.584(2) Angstroem, b = 9.607(3) Angstroem, c = 15.899(4) Angstroem, α = 93.67(3) deg, β = 95.18(3) deg, and γ = 110.17(4) deg.Of the 2989 unique reflections collected, 2541 with Fo > 2.5?(Fo) were used in the solution and refinement of the structure, RF = 0.0642, RwF = 0.0794, and GOF = 2.034.The structure exhibits a linear V-N-C fragment <179.7(5) deg>, short V-N bond <1.707(6) Angstroem>, and small Cp (centroid)-V-Cp (centroid) angle <135.8(3) deg>.For the model complex Cp2VN(C6H5), SCF-Xα-DV calculations show two strong V-N ? bonds in addition to the ? bond.Spin-polarized SCF-Xα-DV calculations predict an aV/aN ratio in close agreement with the experimental ratio.The calculated highest occupied molecular orbital is nonbonding and localized on V with an exchange splitting of 1.52 eV.Cyclic voltammograms of complexes I-IV in CH2Cl2 show quasi-reversible oxidations to 18e vanadium(V) complexes at potentials ca. 750 mV more negative than ferrocene.
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