Isolation of a (Dinitrogen)Tricopper(I) Complex
2014
Murray, Leslie J. | Weare, Walter W. | Shearer, Jason | Mitchell, Alyssa D. | Abboud, Khalil A.
Reaction of a tris(β-diketimine) cyclophane, H₃L, with benzyl potassium followed by [Cu(OTf)]₂(C₆H₆) affords a tricopper(I) complex containing a bridging dinitrogen ligand. rRaman (νN–N = 1952 cm–¹) and ¹⁵N 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). ∇²ρ values for the Cu–N₂ bond critical points are analogous to those for polar closed-shell/closed-shell interactions.
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