Campbell, R., Konar, S., Hunter, S. et al. (2 more authors) (2018) Labile low-valent tin azides: syntheses, structural characterization, and thermal properties. Inorganic Chemistry, 57 (1). pp. 400-411. ISSN 0020-1669
Abstract
The first two examples of the class of tetracoordinate low-valent, mixed-ligand tin azido complexes, Sn(N3)2(L)2, are shown to form upon reaction of SnCl2 with NaN3 and SnF2 with Me3SiN3 in either pyridine or 4-picoline (2, L = py; 3, L = pic). These adducts of Sn(N3)2 are shock- and friction-insensitive and stable at r.t. under an atmosphere of pyridine or picoline, respectively. A new, fast, and efficient method for the preparation of Sn(N3)2 (1) directly from SnF2, and by the stepwise de-coordination of py from 2 at r.t., is reported that yields 1 in microcrystalline form, permitting powder X-ray diffraction studies. Reaction of 1 with a nonbulky cationic H-bond donor forms the salt-like compound {C(NH2)3}Sn(N3)3 (4) which is comparably stable despite its high nitrogen content (55%) and the absence of bulky weakly coordinating cations that are conventionally deemed essential in related systems of homoleptic azido metallates. The spectroscopic and crystallographic characterization of the polyazides 1-4 provides insight into azide-based H-bonded networks and unravels the previously unknown structure of 1 as an important lighter binary azide homologue of Pb(N3)2. The atomic coordinates for 1 and 2-4 were derived from powder and single crystal XRD data, respectively; those for 1 are consistent with predictions made by DFT-D calculations under periodic boundary conditions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 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. |
Keywords: | Azides; Crystal structure; Ligands; Physical and chemical processes; Pyridines |
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: | 22 Dec 2017 09:50 |
Last Modified: | 22 Dec 2023 12:04 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.inorgchem.7b02621 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:125487 |