Smallwood, Z.M., Davis, M.F., Hill, J.G. orcid.org/0000-0002-6457-5837 et al. (2 more authors) (2019) Syntheses, structures, and infrared spectra of the hexa(cyanido) complexes of silicon, germanium, and tin. Inorganic Chemistry, 58 (7). pp. 4583-4591. ISSN 0020-1669
Abstract
The rare octahedral EC6 coordination skeleton type is unknown for complexes with coordination centers consisting of group 14 elements. Here, the first examples of such EC6 species, the hexacoordinate homoleptic cyanido complexes E(CN)62–, E = Si, Ge, Sn, have been synthesized from element halides SiCl4, GeCl4 and SnF4 and isolated as salts with PPN counterions (PPN+ = (Ph3P)2N+) on a scale of 0.2–1 g. Characterization by spectroscopic techniques and by structure determination through single crystal crystallographic methods show that these pseudohalogen complexes have effective octahedral symmetry in solution and in the solid state. Infrared spectra obtained in solution reveal that the T1u symmetric IR-active vibrations in all three complexes have unusually small oscillator strengths. The observed reluctance of Si(CN)62–, Ge(CN)62–, and Sn(CN)62– to form from chloro-precursors was rationalized in terms of Gibbs free energies, which were found by ab initio calculations at the CCSD(T)-F12b/aug-cc-pVTZ(-PP)-F12 level of theory to be small or even positive. The work demonstrates that E(CN)62– complexes of silicon, germanium and tin are in fact stable at room temperature and exist as well-defined units in the presence of noncoordinating counterions. The results add to our understanding of the chemistry of pseudohalogens and structure and bonding.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2019 American Chemical Society. This is an author produced version of a paper subsequently published in Inorganic Chemistry. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 13 Mar 2019 14:20 |
Last Modified: | 19 Nov 2021 12:05 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.inorgchem.9b00150 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:143581 |