Ambiphilic Reactivity of a Phosphane-Functionalized Cycloheptatrienyl−Cyclopentadienyl Zirconium Sandwich Complex

The reactions of the phosphane-functionalized cycloheptatrienyl−cyclopentadienyl sandwich complex [(η7-C7H7)Zr(η5-C5H4PiPr2)] (1) with selenium, [(tht)AuCl] (tht = tetrahydrothiophene) and [(η6-C7H8)W(CO)3] (C7H8 = 1,3,5-cycloheptatriene) afford the complexes [(η7-C7H7)Zr{η5-C5H4P(Se)iPr2}] (2), [(1)2AuCl] (3), and [(1)2W(CO)3] (4). Because of the presence of a Lewis basic phosphane moiety and a Lewis acidic zirconium atom, ambiphilic behavior of the metallo ligand 1 is observed, and the structural characterization of the complexes 2−4 reveals intramolecular secondary Zr−Se (2), Zr−Cl (3), and Zr−O (4) interactions, respectively. In addition, 4 displays an agostic C−H···W interaction with one of the cycloheptatrienyl rings.