BICYCLIC CYCLOPALLADATED COMPLEXES DERIVED FROM N-BENZYL-SUBSTITUTED SCHIFFS BASES

2-Benzylamino-2-penten-4-one (Hacac-bn) reacts with Pd(MeCO2)(2) and [ Pd(MeCO2)(2)(SPr2i)(2)] in benzene at 50 degrees C to give an N,O-chel ated complex, [Pd(acac-bn)(2)] and a bicyclic cyclopalladated complex, [Pd(acac-NCH2C6H4)(SPr2i)], respectively. Diisopropyl sulfide ligand in the latter complex is replaced easily by PPh3, giving [Pd(acac-NCH2 C6H4)(PPh3)]. N-(Salicylidene)benzylamine (Hsal-bn) also reacts simila rly with Pd(MeCO2)(2) and [Pd(MeCO2)(2)(SPr2i)(2)] at 50 degrees C to afford [Pd(sal-bn)(2)] and [Pd(sal-NCH2C6H4)(SPr2i)], respectively. N- (3,5-Dichlorosalicylidene)benzylamine (Hdcsal-bn) reacts with [Pd(MeCO 2)(2)(SPr2i)(2)] and Pd(MeCO2)(2) in the presence of PPh2(OMe) at 50 d egrees C to yield cyclopalladated complexes, [Pd(dcsal-NCH2C6H4)(SPr2i )] and [Pd(dcsal-NCH2C6H4){PPh2(OMe)}], respectively. [Pd(MeCO2)(2)(dm py)(2)] (dmpy = 3,5-dimethylpyridine) reacted with Hdcsal-bn in 1:1 an d 1:2 molar ratios at 50 degrees C to give [Pd(dcsal-bn)(MeCO2)(dmpy)] and [Pd(dcsal-bn)(2)], respectively. The functions of SPr2i and dmpy in these reactions are discussed. (C) 1997 Elsevier Science S.A.