10.1021/acs.inorgchem.9b01159.s001 Clifton L. Wagner Clifton L. Wagner Lizhi Tao Lizhi Tao James C. Fettinger James C. Fettinger R. David Britt R. David Britt Philip P. Power Philip P. Power Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPr<sup><i>i</i></sup><sub>3</sub>)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes American Chemical Society 2019 metal ligand π- interactions 2 displays Bulky Ligand Dipp amide ligands resonance spectrum Cu two-coordinate transition metal amides copper derivatives Wigley ligand First-Row Transition Metal Amido Derivatives 2019-06-12 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Two-Coordinate_Late_First-Row_Transition_Metal_Amido_Derivatives_of_the_Bulky_Ligand_-N_SiPr_sup_i_i_i_sup_sub_3_sub_Dipp_Dipp_2_6-diisopropylphenyl_Effects_of_the_Ligand_on_the_Stability_of_Two-Coordinate_Copper_II_Complexes/8263511 The synthesis and spectroscopic, structural, and magnetic characterization of the quasi-linear metal­(II) bis­(amides) M­{N­(SiPr<sup><i>i</i></sup><sub>3</sub>)­Dipp}<sub>2</sub> [Dipp = C<sub>6</sub>H<sub>3</sub>-2,6-Pr<sup><i>i</i></sup><sub>3</sub>; M = Fe (<b>1</b>), Co (<b>2</b>), or Zn (<b>3</b>)] are described. The magnetic data demonstrate the impact of metal ligand π-interactions on the magnetic properties of these two-coordinate transition metal amides. Disproportionation of the copper­(I) amide species featuring the ligand -N­(SiPr<sup><i>i</i></sup><sub>3</sub>)­Dipp resulted in the decomposition product [(Pr<sup><i>i</i></sup><sub>3</sub>Si)­N­(<i>c</i>-C<sub>6</sub>H<sub>2</sub>-2,6-Pr<sup><i>i</i></sup><sub>2</sub>)]<sub>2</sub> (<b>4</b>). The electron paramagnetic resonance spectrum of the unstable two-coordinate Cu­{N­(SiPr<sup><i>i</i></sup><sub>3</sub>)­Dipp}<sub>2</sub> displays significantly less Cu–N bond covalency than the stable two-coordinate copper­(II) species Cu­{N­(SiMe<sub>3</sub>)­Dipp}<sub>2</sub>. The testing of -N­(SiPr<sup><i>i</i></sup><sub>3</sub>)­Dipp and a range of other, related bulky amide ligands with their copper derivatives highlights the peculiar combination of steric and electronic properties of the Wigley ligand -N­(SiMe<sub>3</sub>)­Dipp that enable it to stabilize the unique two-coordinate copper­(II) complex Cu­{N­(SiMe<sub>3</sub>)­Dipp}<sub>2</sub>.