Protonated oxalyl chloride and the ClCO + cation.

Autor: Steiner S; Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany., Djordjevic K; Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany., Bockmair V; Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany., Hollenwäger D; Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany., Kornath AJ; Department Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany.
Jazyk: angličtina
Zdroj: Acta crystallographica. Section C, Structural chemistry [Acta Crystallogr C Struct Chem] 2024 Dec 01; Vol. 80 (Pt 12), pp. 792-797. Date of Electronic Publication: 2024 Nov 20.
DOI: 10.1107/S2053229624010714
Abstrakt: The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF 5 and DF/SbF 5 . O-Monoprotonated oxalyl chloride was isolated and represents the first example of a protonated acyl chloride. Diprotonated oxalyl chloride is only stable in solution. Salts of the ClCO + cation were synthesized from the reactions of oxalyl chloride or COClF with SbF 5 in 1,1,1,2-tetrafluoroethane (R-134a, CF 3 CFH 2 ). The colourless salts were characterized by low-temperature vibrational spectroscopy, NMR spectroscopy and single-crystal X-ray diffraction. (1,2-Dichloro-2-oxoethylidene)oxidanium hexafluoridoantimonate(V), [C 2 O(OH)Cl 2 ][SbF 6 ], crystallizes in the monoclinic space group P2 1 and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb 3 F 16 ], in the trigonal space group P3 1 , with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO + cation both display very short C-Cl bonds with a strong double-bond character.
(open access.)
Databáze: MEDLINE
Externí odkaz: