Rossman, George R. and Tsay, F.-D. and Gray, Harry B. (1973) Spectroscopic and magnetic properties of heptacyanomolybdate(III). Evidence for pentagonal-bipyramidal and monocapped trigonal-prismatic structures. Inorganic Chemistry, 12 (4). pp. 824-829. ISSN 0020-1669. doi:10.1021/ic50122a024. https://resolver.caltech.edu/CaltechAUTHORS:20140226-072203974
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Abstract
Several salts containing the Mo(CN)_7^(4-) ion have been studied by a variety of spectroscopic and magnetic techniques. Infrared and Raman spectral data together with magnetic susceptibility measurements suggest a pentagonal-bipyramidal (D_(Sh)) structure (2E_1"-(e_1")^3 ground state) for Mo(CN)_7^(4-) in aqueous solutions of K_4Mo(CN)_7•2H_2O. Anhydrous K_4Mo(CN), and solid Cs_4Mo(CN)_7xH_2O also appear to contain pentagonal-bipyramidal anions. Solid K_4Mo(CN)_7•2H_2O, however, exhibits infrared and Raman spectra that differ from the aqueous solution results. The esr spectrum of the dihydrate, which can be observed only below 150ºK, gives gII = 2.103 and g_⊥= 1.973. The g values and a µ_(eff) = 1.73 BM are consistent with a ^2A_1(a_2)^2(a_1)^1 ground state of a monocapped trigonal-prismatic (C_(2v) coordination geometry. Electronic spectral bands at 16,100, 20,900, and 22,500 cm^(-1) in crystalline K_4Mo(CN)_7•2H_2O are assigned respectively to the d-d transitions ^2A_1 → ^2A_2, ^2A_1, → ^2B_2, and ^2A_1, → ^2B_1,. The lowest spin-allowed d-d transition in D_(sh) Mo(CN)_7^(4-), occurs at 24,900 cm^(-1).
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| Additional Information: | © 1973 American Chemical Society. Publication Date: April 1973. This research was supported by the Army Research Office-Durham. We thank Professor A. W. Adamson for stimulating our interest in cyanomolybdate chemistry and for several helpful discussions. | |||||||||
| Group: | UNSPECIFIED, Division of Geological and Planetary Sciences | |||||||||
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| Issue or Number: | 4 | |||||||||
| DOI: | 10.1021/ic50122a024 | |||||||||
| Record Number: | CaltechAUTHORS:20140226-072203974 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20140226-072203974 | |||||||||
| Official Citation: | Spectroscopic and magnetic properties of heptacyanomolybdate(III). Evidence for pentagonal-bipyramidal and monocapped trigonal-prismatic structures George R. Rossman, F. D. Tsay, and Harry B. Gray Inorganic Chemistry 1973 12 (4), 824-829 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 44000 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 26 Feb 2014 16:26 | |||||||||
| Last Modified: | 10 Nov 2021 16:46 |
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