Synthesis and derivatization, structures and transition metal (Mo(0), Fe(II), Pd(II) and Pt(II)) complexes of phenylaminobis(diphosphonite), PhN{P(OC6H4OMe-o)2}2

The synthesis, derivatization and coordination behavior of a new aminobis(diphosphonite), PhN{P(OC6H4OMe-o)2}2 (1) is described. The ligand 1 reacts with H2O2, elemental sulfur or selenium to give the corresponding dichalcogenides PhN{P(E)(OC6H4OMe-o)2}2 (E = O, 2; S, 3; Se, 4) in good yield. Reactions of 1 with Mo(CO)6, Pd(NCCH3)2Cl2 and Pt(COD)Cl2 resulted in the formation of the chelate complexes, Mo(CO)4[PhN{P(OC6H4OMe-o)2}2] (5) and MCl2[PhN{P(OC6H4OMe-o)2}2] (M = Pd,7; M = Pt, 8) whereas in the reaction of 1 with [CpFe(CO)2]2, one of the P–N bonds cleaves due to the metal assisted hydrolysis to give a mononuclear complex, [CpFe(CO){P(O)(OC6H4OMe-o)2}{PhN(H)(P(OC6H4OMe-o)2)}] (6). The molecular structures of 1, 4, 5 and 6 are determined by X-ray studies.