Yb(II) Triple-Decker Complex with the μ-Bridging Naphthalene Dianion [CpBn5Yb(DME)]2(μ-η4:η4-C10H8). Oxidative Substitution of [C10H8]2- by 1,4-Diphenylbuta-1,3-diene and P4 and Protonolysis of the Yb-C10H8 Bond by PhPH2

Two synthetic approaches to the new three-decker Yb(II) complex [(CpYb)-Yb-Bn5(DME)](2)[mu-C10H8] (1) were successfully employed: the reaction of [(CpYb)-Yb-Bn5(DME)(mu-I)](2) (2) with 2 molar equiv of [C10H8](-)center dot K( in DME and the reaction of [YbI(DME)(2)](2)[mu-C10H8] (3) with (CpK)-K-Bn5 in a 1:2 molar ratio in DME. Complex 1 was proved to be a Yb(II) binuclear triple-decker complex containing a dianionic naphthalene ligand bridging two (CpYb)-Yb-Bn5(DME) fragments in a mu-eta(4):eta(4) fashion. An oxidative substitution of (C10H8)(2-) by trans-(1E,3E)-1,4-diphenylbuta-1,3-diene afforded the three-decker Yb(II) complex [(CpYb)-Yb-Bn5(DME)](2)(mu-eta(4):eta(4)-PhCHCHCHCHPh) (4) with a dianionic mu-eta(4):eta(4)-bridging diphenylbutadiene ligand and naphthalene. The reaction of 1 with excess P-4 also occurs with oxidation of (C10H8)(2-), whereas Yb remains divalent. The reaction results in the formation of the trinuclear Yb(II) complex with a mu-bridging P-7(3-) ligand [(CpYb)-Yb-Bn5(DME)](3)(P-7) (5). Protonation of the Yb-C10H8 bond in 1 with PhPH2 (1:2 molar ratio) afforded the dimeric phosphido complex [(CpYb)-Yb-Bn5(THF)(mu(2)-PHPh)](2) (6) in 64% yield, while an attempt to obtain a phosphinidene Yb(II) species by reacting equimolar amounts of 1 and PhPH2 in DME resulted in the isolation of the metallocene complex (Cp2Yb)-Yb-Bn5(DME) (7).