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Octacoordinate metal carbonyls of scandium and yttrium: theoretical calculations and experimental observation
Author(s) -
Xing Xiaopeng,
Wang Jie,
Xie Hua,
Liu Zhiling,
Qin Zhengbo,
Zhao Lijuan,
Tang Zichao
Publication year - 2013
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.6573
Subject(s) - chemistry , scandium , yttrium , dissociation (chemistry) , density functional theory , coordination number , metal , transition metal , bond dissociation energy , crystallography , ligand (biochemistry) , ion , metal carbonyl , agostic interaction , atom (system on chip) , computational chemistry , inorganic chemistry , catalysis , organic chemistry , biochemistry , receptor , computer science , embedded system , oxide
RATIONALE The transition metal carbonyls are among the most important complexes in coordination chemistry. The maximum coordination number in these complexes is seven. Because the cations Sc + and Y + have empty second outermost d orbital subshells, they can possibly bond eight CO ligands, forming the 18‐electron d 10 s 2 p 6 noble gas configuration. The aim of this study is to determine whether the octacoordinate metal carbonyls of Sc + and Y + exist. METHODS The structures and bonding of M(CO) n + (M = Sc and Y, n = 7–9) were studied using Density Functional Theory (DFT) calculations with the functionals of B3LYP and BP86. The cationic complexes from laser ablation of Sc and Y in CO gas were analyzed by time‐of‐flight mass spectrometry. RESULTS The structures of M(CO) n + (M = Sc and Y, n = 7–9) and the bond dissociation energies for the last CO ligand in M(CO) n + (M = Sc and Y, n = 8 and 9) were obtained using DFT calculations. The products in the experiment for both metals include the series MO(CO) n + , MO(H 2 O)(CO) n + and M(CO) n + (M = Sc or Y). The intensities of the MO(CO) n + and MO(H 2 O)(CO) n + ions change gradually with the number of CO ligands, while most M(CO) n + ions are very weak except for three intense ones, Sc(CO) 7 + , Sc(CO) 8 + and Y(CO) 8 + . CONCLUSIONS Comparisons between the theoretical calculations and the experimental observations indicate that eight CO ligands are chemically bonded on the central atom in the singlet state of Sc(CO) 8 + ( 1 A 1 state of D 4 d symmetry) and the singlet and triplet states of Y(CO) 8 + ( 1 A 1 state of D 4d symmetry and 3 A 1g state of O h symmetry). The 1 A 1 states of both Sc(CO) 8 + and Y(CO) 8 + have the 18‐electron d 10 s 2 p 6 noble gas configuration. In M(CO) 9 + (M = Sc or Y), the ninth CO is weakly adsorbed on the external shell. Copyright © 2013 John Wiley & Sons, Ltd.