Yb(II) Triple-Decker Complex with the μ-Bridging Naphthalene Dianion [Cp^Bn5Yb(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

Abstract

Two synthetic approaches to the new three-decker Yb­(II) complex [CpBn5Yb­(DME)]2[μ-C10H8] (1) were successfully employed: the reaction of [CpBn5Yb­(DME)­(μ-I)]2 (2) with 2 molar equiv of [C10H8]−·K in DME and the reaction of [YbI­(DME)2]2[μ-C10H8] (3) with CpBn5K 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 CpBn5Yb­(DME) fragments in a μ-η4:η4 fashion. An oxidative substitution of (C10H8)2– by trans-(1E,3E)-1,4-diphenylbuta-1,3-diene afforded the three-decker Yb­(II) complex [CpBn5Yb­(DME)]2(μ-η4:η4 -PhCHCHCHCHPh) (4) with a dianionic μ-η4:η4-bridging diphenylbutadiene ligand and naphthalene. The reaction of 1 with excess P4 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 μ-bridging P7 3– ligand [CpBn5Yb­(DME)]3(P7) (5). Protonation of the Yb–C10H8 bond in 1 with PhPH2 (1:2 molar ratio) afforded the dimeric phosphido complex [CpBn5Yb­(THF)­(μ2-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 CpBn5 2Yb­(DME) (7).

Recent Advances in Rare‐Earth Polypnictides

“…Moreover, a ytterbium analogue containing P 7 3– trianion was recently reported by Trifonov and co‐workers by employing a Yb(II) triple‐decker complex containing a μ‐bridging naphthalene dianion for the activation of P 4 . These divergent activation outcomes of P 4 by reductive rare earth complexes, leading to cyclo ‐ P 4 2– , cyclo ‐P 3 – , P 8 4– and P 7 3– clusters, collectively illustrated the effect of the trivial variations of rare earth cations and supporting ligand framework on such type of activation.…”

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare‐Earth‐Metal Cyclo‐P3 Complexes

“…AP 4 molecule is formally split in a [ 3 + +1] manner to aP 3 moiety and aP 1 fragment. [6,17] To the best of our knowledge, 2a-c are the first cyclo-P 3 complexes of rare-earth metals.F urthermore, 2a-c are also the first organo-substituted polyphosphides in the category of f-block metals, [15c, 18] and two P À Cb onds have been constructed which is essential for the synthesis of organophosphorus compounds. [7d, 16] This nucleophilic mechanism shows the first P 4 degradation pathway involving rare-earth metal fragments,w hile the rare-earth metalmediated reductive P 4 activation pathway usually generates aggregation products.…”

“…[7d, 16] This nucleophilic mechanism shows the first P 4 degradation pathway involving rare-earth metal fragments,w hile the rare-earth metalmediated reductive P 4 activation pathway usually generates aggregation products. [6,17] To the best of our knowledge, 2a-c are the first cyclo-P 3 complexes of rare-earth metals.F urthermore, 2a-c are also the first organo-substituted polyphosphides in the category of f-block metals, [15c, 18] and two P À Cb onds have been constructed which is essential for the synthesis of organophosphorus compounds. [1,19] To evaluate the coordination behaviors of these novel complexes,G roup 6m etal carbonyl compounds were applied.…”

“…[1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization. [1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization.…”

“…The direct functionalization of white phosphorus (P 4 )t o construct value-added phosphorus-containing compounds is becoming ah ot area because it avoids the use of corrosive chlorine gas and the generation of large amounts of hydrochloric acid. [1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization. Basically,[2+ +2] fragmentation can yield the activated P 2 -containing species A or B,a nd [3+ +1] fragmentation can yield the activated P 1 -containing species or two possible P 3 -containing species C or D (Scheme 1a).…”