Synthesis and Characterization of SF4 Adducts with Polycyclic Amines.
Inorg Chem
; 59(12): 8620-8628, 2020 Jun 15.
Article
in En
| MEDLINE
| ID: mdl-32441932
ABSTRACT
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 21 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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Inorg Chem
Year:
2020
Type:
Article
Affiliation country:
Canada