267895-01-2Relevant academic research and scientific papers
Preparation and structure of phosphonium ions with intramolecular P ← N coordination; Novel diphosphonium salts and ionomer containing backbone hypervalent phosphorus
Carre, Francis H.,Chuit, Claude,Corriu, Robert J. P.,Douglas, William E.,Guy, Daniel M. H.,Reye, Catherine
, p. 647 - 653 (2000)
Starting from R'R2P (R' = 8-dimethylamino-1-naphthyl) containing a donor dimethylamino group, the new phosphonium salts [R'R2P(CH2Ph)]+Br- [R = Me (9) or Ph (10)] and [R'R2P(p-CH2C6H4CH2)PR2R']2+[2Br]2- [R = Ph (12)] have been prepared. An interaction between the N and P atoms is evident from the X-ray crystal structure of 10 the N-P distance being less than the sum of the van der Waals radii of the 2 atoms. The geometry of 10 is that of a monocapped tetrahedron whereas the X-ray crystal structure determination shows essentially regular tetrahedral geometry for the analogous compound without the donor amino group, [(1-Np)Ph2P(CH2Ph)]+Br- (11). Treatment of 1,5-bis(dimethylamino)-2,6-dilithionaphthalene with chlorodiphenylphosphane gave 1,5-bis(dimethylamino)-2,6- bis(diphenylphosphanyl)-naphthalene (8) which in the presence of methyl iodide afforded the diphosphonium salt [1,5-bis(dimethylamino)-2,6- bis(diphenylmethylphosphonium)naphthalene]2+[2I]2- (13). Similarly, treatment of 8 with 1 equivalent of benzyl bromide gave the monophosphonium salt [1,5-bis(dimethylamino)-2-diphenylbenzylphosphonium-6- diphenylphosphanyl-naphthalene]+[Br]- (14) whereas in the presence of 2 equivalents of the same reagent [1,5-bis(dimethylamino)-2,6- bis(diphenylbenzylphosphonium)naphthalene]2+[2 Br]2- (15) was obtained. The ionomer poly([(1,5-bis{dimethylamino}2,6- bis{diphenylphosphonium}naphthalene)-(P,P-p-xylylene)]2+[2 Br]2-) (16), soluble in liquid SO2, was prepared by treatment of 8 with α,α'-dibromo-p- xylene.
