An eight-membered cyclic C,N-bis(germadiyl) bis(ketenimine)
(1998) Organometallics — Vol. 17, n° 8, p. 1517-1522 (1998)
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- The reaction of tert-butyllithium with (fluorodimesitylgermyl)- and (chlorodimesitylgermyl)phenylacetonitrile (4a,b) leads to the lithium salts 5a (X = F) and 5b (X = Cl), which exhibit an ambident character: [> C--C=N <----> > C=C=N-]Li+. Quenching of 5a with triphenylbromomethane affords the germylketenimine 8, Mes(2)FGeC(Ph)=C=NCPh3. H-1 dynamic NMR spectroscopy allows the determination of the activation energy of the nitrogen inversion Delta G* = 9.9 +/- 0.2 kcal/mol. In the absence of a trapping reagent, 5 undergoes an elimination of lithium halide with formation of the eight-membered cyclic C,N-bis(germadiyl) bis(ketenimine) 1, which is the first ring containing two ketenimine moieties. 1 has been characterized by IR (nu(C=C=N) 2015 cm(-1)) and C-13 NMR spectroscopy (170.87 ppm for the sp carbon) and by an X-ray structure determination, which displays a "cyclohexane" type structure in a chair conformation.
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Lee, V., Declercq, J.-P., Ranaivonjatovo, H., Escudie, J., Satge, J., Dubourg, A., Egorov, M., & Nefedov, O. (1998). An eight-membered cyclic C,N-bis(germadiyl) bis(ketenimine). Organometallics, 17(8), 1517-1522. https://doi.org/10.1021/om971014p (Original work published 1998)