Complexes of Formaldehyde and α-Dicarbonyls with Hydroxylamine: FTIR Matrix Isolation and Theoretical Study

The interactions of formaldehyde (FA), glyoxal (Gly) and methylglyoxal (MGly) with hydroxylamine (HA) isolated in solid argon and nitrogen were studied using FTIR spectroscopy and ab initio methods. The spectra analysis indicates the formation of two types of hydrogen-bonded complexes between carbonyl and hydroxylamine in the studied matrices. The cyclic planar complexes are stabilized by O–H⋯O(C), and C–H⋯N interactions and the nonplanar complexes are stabilized by O–H⋯O(C) bond. Formaldehyde was found to form with hydroxylamine, the cyclic planar complex and methylglyoxal, the nonplanar one in both argon and nitrogen matrices. In turn, glyoxal forms with hydroxylamine the most stable nonplanar complex in solid argon, whereas in solid nitrogen, both types of the complex are formed.

Cu(iii)–bis-thiolato complex forms an unusual mono-thiolato Cu(iii)–peroxido adduct

The square-planar complex [bis(toluene-3,4-dithiolato)copper(iii)][NEt3H], characterised by X-ray photoelectron spectroscopy and DFT, fragments in FTICR-MS to form [(toluene-3,4-dithiolato)Cu(iii)(peroxide)]− by reaction with O2.