Infrared spectra and density functional calculations of Cu(CO)1–4+, Cu(CO)1–3, and Cu(CO)1–3− in solid neon

Abstract

Laser-ablated copper atoms, cations, and electrons react with CO molecules to give binary copper carbony neutral complexes as well as cation and anion complexes, which are isolated in solid neon and argon matrices. Based on isotopic substitution as well as density functional calculations of isotopic frequencies, absorptions at 2234.4, 2230.4, 2211.3, and 2202.1 cm−1 in neon are assigned to C–O stretching vibrations of the linear CuCO+ and Cu(CO)2+, trigonal planar Cu(CO)3+, and tetrahedral Cu(CO)4+ cations. The absorptions at 1746.2, 1793.9, and 1838.9 cm−1 in neon and at 1733.4, 1780.8, and 1829.7 cm−1 in argon are assigned to the linear CuCO− and Cu(CO)2−, and trigonal planar Cu(CO)3− anions, respectively. The solid neon observations of Cu(CO)1–3 are 20–9 cm−1 blue shifted from the argon matrix counterparts, which are in agreement with previous thermal copper atom matrix isolation studies. This work provides the first vibrational spectra of Cu(CO)1–4+ and Cu(CO)1–3−.

A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates

“…Analysis and assignment of the IR/Raman data of the [M(CO) n ] moieties: In this section we analyze the experimental IR and Raman spectra of the coinage metal carbonyl compounds from earlier and own work and address their in part confusing and not consistent assignment with the help of a known matrix isolation study [46] and additional quantum chemical calculations with inclusion of scalar relativistic effects.…”

“…Neon matrix [46] A C H T U N G T R E N N U N G [AsF 6 ] À [31] [1-Et-CB 11 F 11 ] À [32] ZSM-5 [89] [AlA C H T U N G T R E N N U N G (OR F ) 4…”

“…Neon matrix [46] A [a] The BP86 functional was used with the aug-cc-pVTZ basis set for oxygen and carbon. Here, relativistic calculation does not mean using a relativistic Hamiltonian, but using an effective core potential [90] for copper that accounts for scalar relativistic effects.…”

“…For detailed information see the Supporting Information. 46 non-classical carbonyl complexes ( Table 2 in the Supporting Information) were plotted against the calculated change of the highest (most blue shifted) IR-active stretching frequency Dñ with respect to the calculated vibrational frequency of free CO at ñ = 2123 cm À1 at the same level ( Figure 14). All species were investigated at the BP86/def2-TZVPP level.…”

“…[43,44] The same holds for the observation of [M(CO) [1][2][3][4] ] + in frozen noble-gas matrices by matrix-isolation IR spectroscopy. [45,46] Table 1 in the Supporting Information gives a further representative overview on coinage metal carbonyl complexes characterized by IR spectroscopy and X-ray crystal-structure determinations.…”