Molecular Structure of a Monomeric, Base-Free Metal(I) Amide, TlN[Si(CH(3))(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. Organomet. 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.
Haaland
Arne
A
Department of Chemistry, University of Oslo, Box 1033 Blindern, N-0315 Oslo, Norway, and Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
Shorokhov
Dmitry J.
DJ
Volden
Hans Vidar
HV
Klinkhammer
Karl Wilhelm
KW