Functionalized cyclodiphosphazanes cis-[tBuNP(OR)]2 (R=C6H4OMe-o, CH2CH2OMe, CH2CH2SMe, CH2CH2NMe2) as neutral 2e, 4e or 8e donor ligands

Cyclodiphosphazanes having donor functionalities such as cis-[tBuNP(OR)]2 (R = C6H4OMe-o (2); R = CH2CH2OMe (3); R = CH2CH2SMe (4); R = CH2CH2NMe2 (5)) were obtained in good yield by reacting cis-[tBuNPCl]2 (1) with corresponding nucleophiles. The reactions of 2–5 with [RuCl2(η6-cymene)]2, [MCl(COD)]2 (M = Rh, Ir), [PdCl2(PEt3)]2 and [MCl2(COD)] (M=Pd, Pt) result in the formation of exclusively monocoordinated mononuclear complexes of the type cis-[{tBuNP(OR)}2MLn-κP] irrespective of the reaction stoichiometry and the reaction conditions. In contrast, 2–5 react with [RhCl(CO)2]2, [PdCl(η3-C3H5)]2, CuX (X=Cl, Br, I) to give homobinuclear complexes. Interestingly, CuX produces both mono and binuclear complexes depending on the stoichiometry of the reactants and the reaction conditions. The mononuclear complexes on treatment with appropriate metal reagents furnish heterometallic complexes.