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DOI: 10.1039/A703192K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3115-3128

Zirconium and hafnium diene and dienyl half-sandwich complexes: synthesis, polymerization catalysis and deactivation pathways. The molecular structures of [M(η3-C3H5)(2,3-Me2 C4H4){η-C5H 3(SiMe3)2-1,3}] (M = Zr or Hf[hair space]) and [Hf(η3-C3H5){ η3-CH2CMeCMeCH2B(C6 F5)3}{η-C5 H3(SiMe2)-1,3}][hair space]

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Gerardo Jiménez Pindado, Mark Thornton-Pett and Manfred Bochmann

Abstract

The reduction of [MCl3Cp″] [M = Zr or Hf; Cp″ = η-C5H3(SiMe3 )2-1,3] with sodium amalgam in the presence of dienes gave the compounds [MCl(diene)Cp″] which are alkylated with MeMgBr or RMgCl (R = allyl) to give [MX(diene)Cp″] (X = CH3 or η3-C3H5; diene = 2,3-dimethylbuta-1,3-diene or isoprene). The reduction of [ZrCl(CHCMeCMeCH)Cp″] with an excess of Na–Hg leads to the binuclear η4(5e)-butadienyl complex [Zr(µ-η1∶η4-C4 H3Me2-2,3)Cp″]2, also formed from [ZrMe(C4H4Me2)Cp″] by methane elimination. The butadiene complex [Zr(η3-CH2CMeCHCH2)(η4 -C4H6)Cp″] is obtained directly from [ZrCl3Cp″] and MeCHCHCH2MgCl. The complexes [M(allyl)(diene)Cp″] react with B(C6F5)3 to give the zwitterionic complexes [Cp″M+(η3-C3H5) {η3-C4H4R1R2 B-(C6F5)3}] which contain a 14-electron [CpM(allyl)2]+ core stabilised by agostic bonding of the B–CH2 methylene hydrogens. These zwitterions catalyse the polymerisation of ethene to high molecular weight polyethene. Catalysts with similar activities are obtained by the activation of [M(allyl)(diene)Cp″] with [CPh3][B(C6F5)4]. The thermal stability of the zwitterionic active species depends strongly on the steric requirements of the dienyl ligands and decreases sharply in the order R1 = R2 = Me > R1 = Me, R2 = H [double greater-than, compressed] R1 = H, R2 = H; i.e. the dimethylbutadiene derivatives are stable at room temperature, while in the latter case decomposition is significant even at -60 °C. The complexes [Zr(η3-CH2CHCHR1){η 3-CH2CR2MeCHCH2B(C6F 5)3}Cp″] (R1 = H, R2 = Me, 9a; R1 = Me, R2 = H, 10) decompose via an unusual C–H activation pathway, with alkene elimination and concomitant migration of a C6F5 substituent from boron to zirconium, to give the catalytically inactive boryldiene complexes [Zr(C6F5){η4-CH2 CR1CHCHB(C6F5)2}Cp ″]. The crystal structures of [M(C3H5)(Me2C4H4 )Cp″] (M = Zr or Hf[hair space]) and [Hf(η3-C3H5){η3 -CH2CMeCMeCH2B(C6F5) 3}Cp″] are reported.

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