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