Gaseous bis(hexamethyldisilylamido)cadmium(II), Cd{N(SiMe 3) 2}, 2, has been studied by electron diffraction at a nozzle temperature of ca. 375K. The diffraction data are consistent with a model including only monomers. By assuming a linear NCdN chain and planar environments about the nitrogen atoms, an equilibrium conformer with a staggered Si 2NCdNSi 2 skeleton ( D 2d symmetry) may be brought into a nice agreement with the data. The large value of the amplitude of vibration for the inter-ligand Si…Si distances, 0.31(10) A, indicates that the ligands undergo large-amplitude vibrations about the NCdN axis. The value of the barrier to internal rotation about this axis is estimated to be in the range 1–2 kcal mol −1. A model with an eclipsed, co-planar Si 2NCdNSi 2 backbone ( D 2h symmetry) could not be brought into agreement with the observed intensity data. Some key parameters, including bond lengths ( τ a ) and valence angles, are: CdN 2.03(2) A, SiN 1.727(7) A, SiC 1.881(3) A; ∠CdNSi 114.0(0.6)°, ∠SiNSi 132.0(1.2)°, ∠NSiC 113.6(1.2)° and ∠SiCH 111.0(1.2) 0 (Parenthesized values denote least-squares standard deviations multiplied by a factor of three). The SiMe, groups are twisted 20(3) 0 away from the reference position typified by one SiC bond of each such group eclipsing the adjacent CdN bond, while the methyl groups themselves are essentially in staggered positions, the value of the relevant twist angle being 8(6) 0.
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