On the nature of spin- and orbital-resolved $Cu^{+}-NO$ charge transfer in the gas phase and at Cu(I) sites in zeolites

Electronic factors essential for NO activation by Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels (natural orbitals for chemical valence). NOCV analysis is performed for three DFT-opti- mized models of Cu(I)–NO site in ZSM-5: [CuNO] ? , (T1)CuNO, and (M7)CuNO. NO as a non-innocent, open- shell ligand reveals significant differences between inde- pendent deformation density components for a and b spins. Four distinct components are identified: (i) unpaired electron donation from NO p k * antibonding orbital to Cu s,d ; (ii) backdonation from copper d yz to p \ * antibonding orbital; (iii) donation from occupied p k and Cu d xz to bonding region, and (iv) donation from nitrogen lone-pair to Cu s,d . Channel (i), corresponding to one-electron bond, shows-up solely for spin majority and is effective only in the interaction of NO with naked Cu ? . Channel (ii) dominates for models b and c: it strongly activates NO bond by populating antibonding p * orbital and weakens the N–O bond in contrast to channel (i), depopulating the antibonding orbital and strengthening N–O bond. This picture perfectly agrees with IR experiment: interaction with naked Cu ? imposes small blue-shift of N stretching frequency while it becomes strongly red-shifted for Cu(I) site in ZSM-5 due to enhanced backdonation.