A comparison of stable carbonyls formed in the gas-phase reaction between group 10 atomic anions and methanol or methoxy radicals: Anion photoelectron spectroscopy and density functional theory calculations on HNiCO−, PdCO−, and PtCO−

Abstract

Articles you may be interested inVibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution J. Chem. Phys. 134, 244503 (2011); 10.1063/1.3603966Addition of water and methanol to Al 3 O 3 − studied by mass spectrometry and anion photoelectron spectroscopy Study of tin-and tin cluster-cyano complexes using anion photoelectron spectroscopy and density functional calculationsThe 3.49 eV photoelectron spectra of HNiCO Ϫ , PdCO Ϫ , and PtCO Ϫ generated from the gas-phase reaction of atomic anions with methanol are presented and interpreted in the context of new density functional calculations. The calculated electron affinities ͑EAs͒ for PdCO ͑0.58 eV͒ and PtCO ͑1.13 eV͒ are in excellent agreement with experimental values ͓0.606͑10͒ and 1.212͑10͒ eV, respectively͔ while for HNiCO, the calculated EA ͑1.64 eV͒ is 0.48 eV lower than the experimental value. However, in all three cases, the vibrational frequencies and spectral profiles are consistent with calculated structures, frequencies, and normal coordinates. HNiCO Ϫ and HNiCO are predicted to be linear, with 1 ⌺ ϩ and 2 ⌬ ground states, respectively. Calculations on PdCO Ϫ agree with recent calculations by Andrews and co-workers ͓J. Phys. Chem. A 104, 3905 ͑2000͔͒ which predict a bent 2 AЈ ground state. The ground state of PtCO Ϫ is calculated to be the linear 2 ⌺ ϩ state. Both PdCO and PtCO are predicted to have 1 ⌺ ϩ ground states. For all species, backdonation of d -electron density into the CO * orbital is an important component of the metal carbonyl bond, with the effect being more pronounced in the anions.

Octacoordinate metal carbonyls of scandium and yttrium: theoretical calculations and experimental observation

“…[2] With the development of techniques for gas-phase experiments and matrix-isolation, more saturated and unsaturated metal carbonyls have been generated and characterized. The typical experimental methods involved generating transition metal carbonyls through reactions of a single metal ion or atom with CO, and then characterizing the products using mass spectrometry, infrared dissociation spectroscopy and photoelectron spectroscopy in the gas phase, [5][6][7][8][9][10][11][12][13] or infrared absorption spectroscopy in matrix. [3,[14][15][16][17][18] At the same time, Density Functional Theory (DFT) calculations combined with the experiments have been effective in predicting the structures and bonding of these complexes.Except a very few special species, [5] most saturated transition metal carbonyls satisfy the 18-electron rule, in which the electrons from the central metal atom and the ligands form the d 10 s 2 p 6 noble gas configuration.…”

Comparison of Nickel-Group Metal Cyanides and Acetylides and Their Anions Using Anion Photoelectron Spectroscopy and Density Functional Theory Calculations

“…In this paper, we report density functional theory (DFT) calculations and anion photoelectron (PE) spectra of a series of group 10 cyanide and acetylide complexes, as a continuation of previous studies on unsaturated group 10 metal complexes formed in gas-phase reactions. [18][19][20] The predominantly ionic cyanide and acetylide complexes discussed in this paper show both similarities and fundamental differences in bonding with the carbonyls studied previously. 20…”

“…Surface plots of the NiCN -orbitals from the calculations are included, along with the 2π orbital of HNiCO for comparison 20. …”

PdnAg(4−n) and PdnPt(4−n) clusters on MgO (100): a density functional surface genetic algorithm investigation

“…This backbonding is known to play a signicant role in the stability of the metal-CO system, impacting upon the structure of the resulting complex. Chatterjee and coworkers performed a gas phase study of group 10 carbonyls with photoelectron spectroscopy (PES) and DFT, 85 showing that the backbonding interaction is strengthened in platinum relative to palladium, due to the better metal d electron overlap with the vacant CO p* orbital, and that this bond is the source of the linearity of PtCO À , while PdCO À is bent. From PES experiments on Ni À (1-3) , Pd À…”