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Octacarbonyl Anion Complexes of the Late Lanthanides Ln(CO) 8 − (Ln=Tm, Yb, Lu) and the 32‐Electron Rule
Author(s) -
Jin Jiaye,
Pan Sudip,
Jin Xiaoyang,
Lei Shujun,
Zhao Lili,
Frenking Gernot,
Zhou Mingfei
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805260
Subject(s) - lanthanide , atomic orbital , chemistry , ground state , covalent bond , valence (chemistry) , crystallography , electronic structure , ion , electron configuration , molecular orbital , metal , photodissociation , singlet state , valence electron , electron , atomic physics , photochemistry , molecule , computational chemistry , excited state , physics , organic chemistry , quantum mechanics
The lanthanide octacarbonyl anion complexes Ln(CO) 8 − (Ln=Tm, Yb, Lu) were produced in the gas phase and detected by mass‐selected infrared photodissociation spectroscopy in the carbonyl stretching‐frequency region. By comparison of the experimental CO‐stretching frequencies with calculated data, which are strongly red‐shifted with respect to free CO, the Yb(CO) 8 − and Lu(CO) 8 − complexes were determined to possess octahedral ( O h ) symmetry and a doublet X 2 A 2u (Yb) and singlet X 1 A 1g (Lu) electronic ground state, whereas Tm(CO) 8 − exhibits a D 4 h equilibrium geometry and a triplet X 3 B 1g ground state. The analysis of the electronic structures revealed that the metal‐CO attractive forces come mainly from covalent orbital interactions, which are dominated by [Ln(d)]→(CO) 8 π backdonation and [Ln(d)]←(CO) 8 σ donation (contributes ≈77 and 16 % to covalent bonding, respectively). The metal f orbitals play a very minor role in the bonding. The electronic structure of all three lanthanide complexes obeys the 32‐electron rule if only those electrons that occupy the valence orbitals of the metal are considered.