摘要:
C hem i cal Communications NUMBER 2/1966 26 JANUARY Complexes of Hexamethylbenzene with Chloro- and Dimethylamino-cyclophosphazenes. Some Alternation of Properties with Change in Ring Size By S. K. DAS, R. A. SHAW, B. C. SbiIrH, and C. P. THAKUR [Department of Chemistry, Birkbeck College (University of London) Mulct Street, London, W.C. 13 AMINOCYCLOPHOSPHAZENES are strong electron donors to protonic and Lewis acids.l? Recently we used phase diagrams to demonstrate complex formation between various amino- and chloro- cyclop~~sphazenes.~ This technique is now ex- tended to a study of compound formation between hexamethylbenzene, a typical strong n-donor, and chloro- and dimethylamino-cyclophosphazenes hav- ing six-, eight-, ten-, and twelve-membered rings. The results are summarized in the Table.each form one complex; the cyclo-tetra- and -hexa- phosphazenes each form two complexes. Dimethylaminocyclophosphazenes are strong donors. It is of particular interest that the cyclo- tetra- and -hexa-phosphazenes behave also as electron-acceptors and both form complexes with hexamethylbenzene. Complexes of cyclo-tri- and -penta-phosphazenes are not observed under similar conditions. These are believed to be the first examples of TABLE Composition of Complexes n C6Me6: N,P,C1,, M.p. ("c) C,Me,: N,P,(NMe,),, M.p. ("c) 3 2: 1 149 4 2: 1 152 2: 1 156 1: 1 136 5 2: 1 141 6 1 : 1 125 1: 1 178 1:2 110 - - - - Chlorocyclophosphazenes are weak or negligible donors towards protons or iodine12p* but strong acceptors which form complexes with hexamethyl- benzene. The cyclo-tri- and -penta-phosphazenes is being extended to solution. properties of cyclophosphazenes alternating with ring size. These phase diagrams give indications only of behaviour in the solid state, and the work (Received, December ZOth, 1965 ; COP;L. 78 4.) S. K. Ray and R. A. Shaw, Chem. and Ind., 1961, 1173; D. Feakins, W. A. Last, and R. A . Shaw, Chetn. aiad S. K. Das, R. A. Shaw, B. C. Smith, W. A. Last, and F. B. G. Wells, Chem. and Ind., 1963, 866, S. K. Das, R. A. Shaw, and B. C. Smith, Chem. Comm., 1965, 176. D. Feakins, W. A. Last, N. Neemuchwala, and R. A. Shaw, J . Chem. SOC., 1965, 2804. I n d . , 1962, 510; J . Chem. SOC., 1964, 4464.
ISSN:0009-241X
DOI:10.1039/C19660000033
出版商:RSC
年代:1966
数据来源: RSC