IR spectroscopic characterization of [M,C,2H]+ (M = Ru and Rh) products formed by reacting 4d transition metal cations with oxirane: Spectroscopic evidence for multireference character in RhCH2+

Abstract

A combination of infrared multiple-photon dissociation (IRMPD) action spectroscopy and quantum chemical calculations was employed to investigate the [M,C,2H]⁺ (M = Ru and Rh) species. These ions were formed by reacting laser ablated M⁺ ions with oxirane (ethylene oxide, c-C₂H₄O) in a room-temperature ion trap. IRMPD spectra for the Ru species exhibit one major band and two side bands, whereas spectra for the Rh species contain more distinct bands. Comparison with density functional theory (DFT), coupled-cluster (CCSD), and equation-of-motion spin–flip CCSD (EOM-SF-CCSD) calculations allows assignment of the [M,C,2H]⁺ structures. For the spectrum of [Ru,C,2H]⁺, a combination of HRuCH⁺ and RuCH₂⁺ structures reproduces the observed spectrum at all levels of theory. The well-resolved spectrum of [Rh,C,2H]⁺ could not be assigned unambiguously to any calculated structure using DFT approaches. The EOM-SF-CCSD calculations showed that the ground-state surface has multireference electronic character, and symmetric carbenes in both the ¹A₁ and ³A₂ states are needed to reproduce the observed spectrum.