Gerken, Michael

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Synthesis and characterization of SF4 adducts with polycyclic amines
(American Chemical Society, 2020) Kostiuk, Nathan; Goettel, James T.; Gerken, Michael
Chalcogen-bonding interactions of SF4 with the polycyclic amines DABCO (C6H12N2) and HMTA (C6H12N4) were studied by low-temperature Raman spectroscopy and X-ray crystallography, revealing the 2:1 adducts C6H12N2·2SF4 and C6H12N4·2SF4 obtained from SF4 solvent. In C6H12N2·2SF4, the sulfur in each SF4 molecule is pentacoordinate with each SF4 coordinated by a single amine group, whereas C6H12N4·2SF4 forms a one-dimensional coordination polymer with three of the four nitrogen atoms in HMTA exhibiting N---S chalcogen bonds: one terminal N---SF4 and one experimentally unprecedented bridging N---(SF4)---N moiety. Solvolysis of C6H12N2·2SF4 by HF yielded crystals of [C6H12N2H]+2F–[SF5]−·6SF4, in which SF4 acts as a chalcogen-bond donor toward N as well as F. Solvolysis of C6H12N4·2SF4 resulted in the formation of the monoprotonated HMTA salt [C6H12N4H]+[HF2]−·SF4. Excess HF also led to isolation of monoprotonated HTMA, as seen in the crystal structure of the [C6H12N4H]+[H2F3]−·HF salt. The reaction of bicyclic, monobasic quinuclidine with SF4 and HF gave [C7H13NH]+F–·3.5SF4, which contains N–H---F–---SF4 interactions, as well as an interstitial, disordered SF4 molecule.