| Abstract: | Diphenyldichalcogenides (PhE)2 (E = Te, Se) react with Fe(0)-phenylchalcogenolate PPN] PhEFe(CO)4] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- PPN]Fe(CO)3(TePh)n(ScPh)3-n] (n = 1, 2). Reactions of PPN]REFe(CO)4] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products PPN]PhEFe(CO)4] (E=Te, Se, S). The compounds Fe(CO)3(TePh)(ScPh)2]? (l) and Fe(CO)3(TePh)2 (2) crystallize in the isomorphous monoclinic space group C2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and Rw = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and Rw = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN+ and anions of Fe(CO)3(TcPh)u(ScPh)3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions. |
