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Preparation And Structure Of Phosphonium Ions With Intramolecular P ← N Coordination; Novel Diphosphonium Salts And Ionomer Containing Backbone Hypervalent Phosphorus
Author(s) -
Carré Francis H.,
Chuit Claude,
Corriu Robert J. P.,
Douglas William E.,
Guy Daniel M. H.,
Reyé Catherine
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200004)2000:4<647::aid-ejic647>3.0.co;2-n
Subject(s) - chemistry , phosphonium , intramolecular force , bromide , medicinal chemistry , phosphonium salt , tetrahedral molecular geometry , naphthalene , iodide , crystal structure , hypervalent molecule , salt (chemistry) , methyl iodide , crystallography , stereochemistry , polymer chemistry , reagent , inorganic chemistry , organic chemistry
Starting from R′R 2 P (R′ = 8‐dimethylamino‐1‐naphthyl) containing a donor dimethylamino group, the new phosphonium salts [R′R 2 P(CH 2 Ph)] + Br – [R = Me ( 9 ) or Ph ( 10 )] and [R′R 2 P( p ‐CH 2 C 6 H 4 CH 2 )PR 2 R′] 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)Ph 2 P(CH 2 Ph)] + 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)‐2diphenylbenzylphosphonium‐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 SO 2 , was prepared by treatment of 8 with α,α′‐dibromo‐ p ‐xylene.