Synthesis of eta~6-arene complexes molybdenum containing beta-ketophosphine and related P,O mixed donor ligands

摘要

The reactions of the ligands Ph_2PCH_2C(O)R (R = Ph, NPh_2) with the eta~6-arene molybdenum complexes [Mo(eta~3-C_3H_5)(mu-Cl)(eta~6-C_6H_5R)]_2 (R = H, Me) have been investigated. A series of complexes in which the keto-or amidophosphine acts as a monodentate P ligand or as a natural or anionic P,O chelating ligand have been synhesised and charactreised. The crystal structures of the compounds [Mo(eta~3-C_3H_5)Cl(eta~6-C_6H_5Me){Ph_2PCH_2C(O)Ph}], [Mo(eta~3-C_3H_5){Ph_2PCH_2C(O)NPh_2-kappa~2P,O}(eta~6-C_6H_5Me)][PF_6] and [Mo(Ph_2PCH-C(-O)Ph-kappa~2P,O}_2(eta~6-C_6H_5R)] (R = H, Me) hve been determined. Interesting differences in the reactivity of the ketophosphine ligand versus the amidophosphine ligand were discovered and an unprecedented hydrogen-deuterium exchange of methylene and olefinic protons has been observed for the coordinated neutral or anionic ketophosphine ligands.