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Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPri3)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

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journal contribution
posted on 12.06.2019 by Clifton L. Wagner, Lizhi Tao, James C. Fettinger, R. David Britt, Philip P. Power
The synthesis and spectroscopic, structural, and magnetic characterization of the quasi-linear metal­(II) bis­(amides) M­{N­(SiPri3)­Dipp}2 [Dipp = C6H3-2,6-Pri3; M = Fe (1), Co (2), or Zn (3)] 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(SiPri3)­Dipp resulted in the decomposition product [(Pri3Si)­N­(c-C6H2-2,6-Pri2)]2 (4). The electron paramagnetic resonance spectrum of the unstable two-coordinate Cu­{N­(SiPri3)­Dipp}2 displays significantly less Cu–N bond covalency than the stable two-coordinate copper­(II) species Cu­{N­(SiMe3)­Dipp}2. The testing of -N­(SiPri3)­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(SiMe3)­Dipp that enable it to stabilize the unique two-coordinate copper­(II) complex Cu­{N­(SiMe3)­Dipp}2.