Structural Evolution of Homoleptic Heterodinuclear Copper–Nickel Carbonyl Anions Revealed Using Photoelectron Velocity-Map Imaging

Abstract

The homoleptic heterodinuclear copper-nickel carbonyl anions CuNi(CO)n(-) (n = 2-4) were generated in a pulsed-laser vaporization source and investigated using photoelectron velocity-map imaging spectroscopy. The electron affinities of CuNi(CO)2 (2.15 ± 0.03 eV), CuNi(CO)3 (2.30 ± 0.03 eV), and CuNi(CO)4 (1.90 ± 0.04 eV) were deduced from the photoelectron spectra. Theoretical calculations at the B3LYP level were carried out to elucidate the structures and the electronic properties of CuNi(CO)n(0/1-) (n = 1-4) and to support the experimental observations. Comprehensive comparisons between experiments and calculations suggest that there is a turnover point of the absorption site during the progressive carbonylation process. The carbonyl groups are determined to be preferentially bonded to the nickel atom. When the nickel center satisfies the 18-electron configuration, the copper atom starts to adsorb additional CO molecules. These results will shed light on the bonding mechanisms of the heterometallic carbonyl clusters.

Ligand-Mediated Reactivity in CO Oxidation of Niobium–Nickel Monoxide Carbonyl Complexes: The Crucial Roles of the Multiple Adsorption of CO Molecules

“…The experimental observations of abrupt band shift, together with the spectral similarities and differences, imply the occurrence of structural evolution during the consecutive CO adsorption progress. The similar band shift correlated with geometric evolution has been detected in our previous study of homoleptic heterodinuclear copper–nickel carbonyl anions using photoelectron velocity-map imaging …”

“…The similar band shift correlated with geometric evolution has been detected in our previous study of homoleptic heterodinuclear copper−nickel carbonyl anions using photoelectron velocity-map imaging. 45 To gain insight into the geometry and reactivity of these complexes, we have carried out density functional theory (DFT) calculations at the BP86 level on the NbNiO(CO) n − (n = 4−8) series. Theoretical calculations indicate that the lowestlying isomers of NbNiO(CO) n − (n = 4−8) are closed-shell species (Table S1 in the Supporting Information).…”

Infrared Photodissociation Spectroscopy of Heteronuclear Arsenic–Iron Carbonyl Cluster Anions

“…Natural bond orbital (NBO) analysis was performed to study the atomic electronic charge distributions and bonding character of the cluster anions. The hybrid functional B3LYP, pure functional BP86, and meta -GGA functional TPSS are among the most popular density functionals and have proven to provide reliable predictions on the structures and vibrational frequencies of arsenic clusters and transition-metal-containing clusters. ,− Throughout the calculation process, the three functionals agreed well in their isomer location predictions. To be consistent with our previous studies, − the optimized structures and the frequencies obtained using the B3LYP functional were used unless stated otherwise.…”

Photoelectron Velocity Map Imaging Spectroscopic and Theoretical Study of Heteronuclear MNi(CO)7– (M = V, Nb, Ta)

“…14−16 As for later transition metal−nickel carbonyls, MNi(CO) n − (M = Ag, Cu), the carbonyl groups are determined to be preferentially bonded to the nickel atom until the nickel center satisfies the 18-electron configuration then additional CO molecules start to bind with the copper atom. 17,18 Herein, we conduct a systematic investigation on the heterodinuclear group 5-nickel clusters MNi(CO) 7…”