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Spectroscopic and magnetic properties of heptacyanomolybdate(III). Evidence for pentagonal-bipyramidal and monocapped trigonal-prismatic structures

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).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.acs.org/doi/abs/10.1021/ic50122a024PublisherArticle
http://dx.doi.org/10.1021/ic50122a024DOIArticle
ORCID:
AuthorORCID
Rossman, George R.0000-0002-4571-6884
Gray, Harry B.0000-0002-7937-7876
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.
Funders:
Funding AgencyGrant Number
Army Research Office (ARO)UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics4240
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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