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PrB 7 − : A Praseodymium‐Doped Boron Cluster with a Pr II Center Coordinated by a Doubly Aromatic Planar η 7 ‐B 7 3− Ligand
Author(s) -
Chen TengTeng,
Li WanLu,
Jian Tian,
Chen Xin,
Li Jun,
Wang LaiSheng
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201703111
Subject(s) - delocalized electron , praseodymium , chemistry , crystallography , unpaired electron , electronic structure , cluster (spacecraft) , boron , ground state , electron , x ray photoelectron spectroscopy , center (category theory) , atomic physics , molecule , inorganic chemistry , physics , computational chemistry , nuclear magnetic resonance , organic chemistry , quantum mechanics , computer science , programming language
The structure and bonding of a Pr‐doped boron cluster (PrB 7 − ) are investigated using photoelectron spectroscopy and quantum chemistry. The adiabatic electron detachment energy of PrB 7 − is found to be low [1.47(8) eV]. A large energy gap is observed between the first and second detachment features, indicating a highly stable neutral PrB 7 . Global minimum searches and comparison between experiment and theory show that PrB 7 − has a half‐sandwich structure with C 6v symmetry. Chemical bonding analyses show that PrB 7 − can be viewed as a Pr II [η 7 ‐B 7 3− ] complex with three unpaired electrons, corresponding to a Pr (4f 2 6s 1 ) open‐shell configuration. Upon detachment of the 6s electron, the neutral PrB 7 cluster is a highly stable Pr III [η 7 ‐B 7 3− ] complex with Pr in its favorite +3 oxidation state. The B 7 3− ligand is found to be highly stable and doubly aromatic with six delocalized π and six delocalized σ electrons and should exist for a series of lanthanide M III [η 7 ‐B 7 3− ] complexes.