Infrared Spectrum of the Hyponitrite Dianion, N2O22-, Isolated and Insulated from Stabilizing Metal Cations in Solid Neon

Abstract

Co-deposition of laser-ablated metals with NO in excess neon at 4 K produced new 1060.8 ′ 0.4 and 1052.6 ′ 0.2 cm - 1 absorptions, which almost disappear on annealing to 9 K and reappear in part on ultraviolet irradiation. These absorptions shift with 1 5 N 1 6 O and 1 5 N 1 8 O substitution as fundamental N-O vibrations and exhibit 1:2:1 triplet bands with 1 4 N 1 6 O + 1 5 N 1 6 O and 1 5 N 1 6 O + 1 5 N 1 8 O mixtures, which demonstrates the involvement of two equivalent NO oscillators. The above absorptions are assigned to N 2 O 2 2 - isolated and insulated from metal stabilizing cations in two solid neon matrix configurations. The blue shift from the 1028.5 cm - 1 solid argon band position for this species is larger than found for most small molecules and anions, which is consistent with a dianion. The photochemistry in laser-ablated gold experiments suggests the involvement of N 2 O 2 - in electron-transfer processes to form N 2 O 2 2 - .