Bridged Dinuclear Tripodal Tris(amido)phosphane Complexes of Titanium and Zirconium as Diligating Building Blocks for Organometallic Polymers

摘要: Appropriate bridging ligands allow for the preparation of bimetallic titanium and zirconium precursors to transition-metal-containing polymers using formally trianionic P(CH2NArR)3 ligand (where ArR = Ph, 3,5-Me2C6H3 a b, respectively). Lithiation known amidophosphane P(CH2NHArR)3 (1a,b) with 3 equiv. nBuLi cleanly provided diethyl ether adducts P(CH2NArR)3Li3(OEt2)1.5 (2a,b). The THF adduct P(CH2NPh)3Li3(THF)5 (2a-THF) was characterized by X-ray crystallography. Protonolysis reactions were used prepare mononuclear complexes P(CH2NArR)3TiOC6H4tBu (4a,b) dinuclear species [P(CH2NPh)3TiNMe2]2-μ-4,4′{O[3,3′,5,5′-(C6H2Me2)2]O} (5a), [P(CH2NPh)3Ti]2(μ-O) (6a), P(CH2N-3,5-Me2C6H3)3Ti-μ-O-Ti(NMe2)3 (7b), from P(CH2NArR)3TiNMe2. 1a,b Zr(NEt2)4 afforded metal type P(CH2NArR)3ZrNEt2 (8a,b). chloride P(CH2NArR)3ZrCl(THF) (9a,b) prepared treatment HNEt3Cl 1 or 2. 9a,b reacted cyclopentadienyllithium (C5H5Li) produce P(CH2NArR)3ZrCp (10a,b), which also lithium salts 2a,b CpZrCl3. dilithium salt fulvalene dianion (Li2C10H8) reacts trans-[P(CH2NArR)3Zr]2(μ-η5:η5-C10H8) respectively. facile bridged illustrated reaction 6a half an equivalent [Rh(CO)2(μ-Cl)]2, precipitated polymeric Cl(CO)Rh[P(CH2NPh)3Ti]2(μ-O). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)