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>.