Ligand transfer reactions between Schiff base divalent group 14 element species and titanium, nickel, boron, and phosphorus halides

Reactions of the inorganic complexes TiCl(4), NiCl(2), BF(3), PCl(3), and (Y)PCl(3) (Y = O, S) Cp(2)-TiCl(2), and t-BuPCl(2) with the Schiff base divalent group 14 element species (L(2))M (1-3: L(2) = N,N'-bis(salicylidene)ethylenediamine (Salen), M = Ge (1), Sn (2); L(2) = (R,R)-(-)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, M = Pb (3)) have been investigated. TiCl(2) and Cp(2)TiCl(2) afforded the ionic [ClTi(L(2))](+)[MCl(3)](-) (4) and the neutral Cp(Cl)Ti(L(2)) (5) complexes, respectively. With NiCl(2). DPPE (DPPE = 1,2-bis(diphenylphosphino)ethane) and (Salen)Sn as starting materials, substitution of tin led to the complex (Salen)Ni . SnCl(2) (7). The linear diboron compound F(2)B(Salen)BF(2) (9) together with the complex (Salen)Sn . SnF(2) (10) were produced on reaction of BF(3). Me(2)O with (Salen)Sn. With t-BuPCl(2) and PCl(3), the phosphite t-BuP(L(2)) (11) and the phosphocation [(L(2))P](+) (12) together with the anion [MCl(3)](-) (9) were obtained, respectively. The phosphoryl and thiophosphoryl chlorides (Y)PCl(3) (Y = O,S) yielded the dinuclear dimeric phosphoranes (Y)P(C1(Salen)P(Y)(C)(Salen) (Y = O (13), S (14)). The crystal structure of 3 was determined by X-ray structure analysis.