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Mo 2 B 4 O 9 —Connecting Borate and Metal‐Cluster Chemistry
Author(s) -
Schmitt Martin K.,
Janka Oliver,
Pöttgen Rainer,
Benndorf Christopher,
de Oliveira Marcos,
Eckert Hellmut,
Pielnhofer Florian,
Tragl AmadeusSamuel,
Weihrich Richard,
Joachim Bastian,
Johrendt Dirk,
Huppertz Hubert
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201701891
Subject(s) - delocalized electron , boron , crystallography , chemistry , molybdenum , raman spectroscopy , diamagnetism , tetrahedron , cluster (spacecraft) , metal , crystal structure , atomic orbital , molecular orbital , inorganic chemistry , molecule , electron , magnetic field , physics , programming language , organic chemistry , quantum mechanics , computer science , optics
We report on the first thoroughly characterized molybdenum borate, which was synthesized in a high‐pressure/high‐temperature experiment at 12.3 GPa/1300 °C using a Walker‐type multianvil apparatus. Mo 2 B 4 O 9 incorporates tetrahedral molybdenum clusters into an anionic borate crystal structure—a structural motif that has never been observed before in the wide field of borate crystal chemistry. The six bonding molecular orbitals of the [Mo 4 ] tetrahedron are completely filled with 12 electrons, which are fully delocalized over the four molybdenum atoms. This finding is in agreement with the results of the magnetic measurements, which confirmed the diamagnetic character of Mo 2 B 4 O 9 . The two four‐coordinated boron sites can be differentiated in the 11 B MAS‐NMR spectrum because of the strongly different degrees of local distortions. Experimentally obtained IR and Raman bands were assigned to vibrational modes based on DFT calculations.