Dealkylation reactions of dialkylaminomethylferrocenes with cyclic chlorocarbaphosphazene, (ClCN)(2)(Cl2PN)

Dialkylaminomethylferrocenes, FcCH(2)NRR' (NRR'=NMe2)(1), NEt2 (2), N(CH2CH =CH2)(2), (3), N(CH2CH2)(2)O (4), N(Me)(CH2Ph) (5) and N(Me)(c-C6H11) (6) ( Fe = Ferrocenyl) were synthesized by the reaction of ferrocene with the cor responding diamines, RR'NCH2NRR'. The identity of 3 was further confirmed b y X-ray structural analysis of its hydrochloride, FcCH(2)NH (CH2CH=CH2)(2)( +) Cl- (7). Reactions of compounds 1-6 were carried out with tetrachlorodic arbaphosphatriazene, (ClCN)(2)(Cl2PN) in diethylether medium at room temper ature or in refluxing toluene. The amines 1, 2, 4, 5 and 6 were found to un dergo a facile C-N bond cleavage at the bridging methylene group irrespecti ve of the nature of substituents on the nitrogen. The cleaved dialkylamino groups were found to substitute regiospecifically at the ring carbon atoms of the carbaphosphazene, yielding the dialkylamino substituted carbaphospha zenes [(RR'N)CN](2),(Cl2PN) 8-12. The X-ray crystal structure of the substi tuted carbaphosphazene (Me2NCN)(2)(Cl2PN) 8 has also been determined. (C) 1 999 Elsevier Science S.A. All rights reserved.