We thank Prof. A. I. Boldyrev, Dr. Jun Li, and Dr. Tom Waters for valuable discussions. This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, U.S. Department of Energy (DOE) under grant number DE-FG02-03ER15481 (catalysis center program) and was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, operated for DOE by Battelle. Calculations were performed at the EMSL Molecular Science Computing Facility.
Observation of d-Orbital Aromaticity†
Article first published online: 17 OCT 2005
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 44, Issue 44, pages 7251–7254, November 11, 2005
How to Cite
Huang, X., Zhai, H.-J., Kiran, B. and Wang, L.-S. (2005), Observation of d-Orbital Aromaticity. Angew. Chem. Int. Ed., 44: 7251–7254. doi: 10.1002/anie.200502678
- Issue published online: 8 NOV 2005
- Article first published online: 17 OCT 2005
- Manuscript Received: 29 JUL 2005
- cluster compounds;
- density functional calculations;
- metal–metal interactions;
- photoelectron spectroscopy
The metal oxide clusters [W3O9]−and [Mo3O9]− were studied by photoelectron spectroscopy and theoretical calculations, which show that [W3O9] and [Mo3O9] both have a D3h structure with a low-lying unoccupied molecular orbital formed from the metal d orbitals. Occupation of this orbital by one or two electrons leads to aromatic anions (see picture) with strong three-center, one-electron and three-center, two-electron metal–metal bonds, respectively.