Inorganic Chemistry, Vol.38, No.6, 1118-1120, 1999
Molecular structure of a monomeric, base-free metal(I) amide, TlN[Si(CH3)(3)](2), by gas electron diffraction and by density functional theory and ab initio MP2 calculations
Thallium bis(trimethylsilyl)amide is a monomer in the gas phase. The molecular symmetry is C-2, the Tl-N bond length is 214.8(12) pm by gas electron diffraction as compared to about 258 pm in the crystalline dimer (Klinkhammer, K. W.; Henkel, S. J. Organamet. Chem. 1994, 480, 167). Structure optimization by DFT or ab initio (MP2) calculations with the ECP basis set on the Tl atom fails to reproduce the experimental Tl-N bond distance unless the 5s,5p,5d electrons on the metal are described explicitly and the atomic basis set includes both polarization and diffuse functions.