Publication details

Syntéza a struktura donory stabilizovaných kationtů [B.POX2]+, [B2.POX]2+ a [B3.PO]3+ (X = F, Cl, Br, B = 4-dimethylaminopyridin)

Title in English Synthesis and Structure of Donor-Stabilized Cations [B.POX2]+, [B2.POX]2+ a [B3.PO]3+ (X = F, Cl, Br, B = 4-dimethylaminopyridin)
Authors

ROVNANÍK Pavel TARABA Jan ČERNÍK Miloš

Year of publication 2003
Type Article in Proceedings
Conference Chemické Listy
MU Faculty or unit

Faculty of Science

Citation
Field Inorganic chemistry
Keywords Phosphoryl halides;Lewis bases; donor-stabilized cations
Description It has been reported that 4-dimethylaminopyridine /B/ reacts with POCl3 to produce a solid 3:1 adduct with a proposed ionic structure of tris (onio)-substituted phosphoryl chloride [OP(B)3][Cl]3. In the course of a reinvestigation of this reaction, however, we soon realized that its end product has another composition and an X-ray diffraction study of the obtained compound revealed the structure of [(B)2PO2]Cl. If the N-trimethylsilyl-4-dimethylaminopyridinium trifluoromethanesulfonate was used instead of free base, reactions with POCl3 or POBr3 could be better controlled and the trifluoromethanesulfonate of the donor-stabilized cations [(B)POCl2]+, [(B)POBr2]+, {(B)2POCl]2+ and [(B)3PO]3+ were obtained. Owing to the markedly lowered reactivity of P-F bonds,in analogous reactions with POF2Cl and POFCl2 the fluorine atoms are not substituted for B, and the salts with cations [(B)POF2]+ and [(B)2POF]2+, respectively, are formed.
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