Publication Date:
2016-03-23
Description:
The heteronuclear metal carbonyl anions M Ni(CO) 3 − ( M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral M Ni(CO) 3 ( M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C–O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm −1 for MgNi(CO) 3 , CaNi(CO) 3 , and AlNi(CO) 3 , respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls M Ni(CO) 3 −1/0 , resulting in the formation of the Ni(CO) 3 motif. Ni remains the 18-electron configuration for MgNi(CO) 3 and CaNi(CO) 3 neutrals, but not for AlNi(CO) 3 . This is different from the homobinuclear nickel carbonyl Ni–Ni(CO) 3 with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.
Print ISSN:
0021-9606
Electronic ISSN:
1089-7690
Topics:
Chemistry and Pharmacology
,
Physics
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