Isolation
of a (Dinitrogen)Tricopper(I) Complex
- Publication date
- Publisher
Abstract
Reaction of a tris(β-diketimine)
cyclophane, H<sub>3</sub><b>L</b>, with benzyl potassium followed
by [Cu(OTf)]<sub>2</sub>(C<sub>6</sub>H<sub>6</sub>) affords a tricopper(I)
complex containing
a bridging dinitrogen ligand. rRaman (ν<sub>N–N</sub> = 1952 cm<sup>–1</sup>) and <sup>15</sup>N NMR (δ
= 303.8 ppm) spectroscopy confirm the presence of the dinitrogen ligand.
DFT calculations and QTAIM analysis indicate minimal metal-dinitrogen
back-bonding with only one molecular orbital of significant N2(2pπ*)
and Cu(3dπ)/Cu(3dσ) character (13.6% N, 70.9% Cu). ∇<sup>2</sup>ρ values for the Cu–N<sub>2</sub> bond critical
points are analogous to those for polar closed-shell/closed-shell
interactions
