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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
journal contribution
posted on 2019-06-12, 00:00 authored by Clifton L. Wagner, Lizhi Tao, James C. Fettinger, R. David Britt, Philip P. PowerThe 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.