512163-89-2

Upstream product

• 512164-12-4 (C₅H₄Me)2Zr(O(t)Bu)Me 
• 68193-38-4 bis(methylcyclopentadienyl)zirconium dimethyl 
• 75-65-0 tert-butyl alcohol 

Downstream Products

• 512163-92-7 [(C₅H₄Me)2Zr(O(t)Bu)(ethylene)][B(C₆F₅)4] 
• 900534-66-9 [(C₅H₄Me)2Zr(O(t)Bu)(3,3-dimethyl-1-butene)][B(C₆F₅)4] 
• 900534-97-6 [(C5H4Me)2Zr(O(t)Bu)(η1-ethyl vinyl ether)][B(C6F5)4] 
• 775322-77-5 [(C₅H₄Me)2Zr(O(t)Bu)(propargyltrimethylsilane)][B(C₆F₅)4] 
• 775322-79-7 [(C₅H₄Me)2Zr(O(t)Bu)(allyltrimethylsilane)][B(C₆F₅)4] 
• 512163-96-1 [Cp'Zr(O(t)Bu)(HCCMe)][B(C₆F₅)4] 
• 512163-98-3 [(C₅H₄CH₃)2Zr(OC(CH₃)3)(CH₃CCCH₃)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[(C₅H₄CH₃)2Zr(OC(CH₃)3)(CH₃CCCH₃)]B(C₆F₅)4 
• 512164-10-2 [(C₅H₄Me)2Zr(O(t)Bu)(cis-2-butene)][B(C₆F₅)4] 
• 900534-88-5 [(C₅H₄Me)2Zr(O(t)Bu)(cyclopentene)][B(C₆F₅)4] 
• 900188-24-1 [(C₅H₄CH₃)2Zr(OC(CH₃)3)(C₄H₈O)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[(C₅H₄CH₃)2Zr(OC(CH₃)3)(C₄H₈O)]B(C₆F₅)4 
• 900534-69-2 [(C₅H₄Me)2Zr(O(t)Bu)(1,5-hexadiene)][B(C₆F₅)4] 
• 512164-07-7 [(C₅H₄Me)2Zr(O(t)Bu)(1-hexene)][B(C₆F₅)4] 
• 775322-81-1 [(C₅H₄Me)2Zr(O(t)Bu)(4,4-dimethyl-1-pentene)][B(C₆F₅)4] 
• 900534-80-7 [(C₅H₄Me)2Zr(O(t)Bu)(vinylferrocene)][B(C₆F₅)4] 

Relevant academic research and scientific papers

Nonchelated d0 zirconium-alkoxide-alkene complexes

The reaction of Cp′2Zr(OtBu)Me (Cp′ = C5H4Me) and [Ph3C][B(C6F 5)4] yields the base-free complex [Cp′ 2Zr(OtBu)][B(C6F5)4] (6), which exists as Cp′2Zr(OtBu)(CIR)+ halocarbon adducts in CD2Cl2 or C6D 5Cl solution. Addition of alkenes to 6 in CD2Cl 2 solution at low temperature gives equilibrium mixtures of Cp′2- Zr(OtBu)(alkene)+ (12a-l), 6, and free alkene. The NMR data for 12a-l are consistent with unsymmetrical alkene bonding and polarization of the alkene C=C bond with positive charge buildup at Cint and negative charge buildup at Cterm. These features arise due to the lack of d-π* back-bonding. Equilibrium constants for alkene coordination to 6 in CD2Cl2 at -89 °C, K eq = [12][6]-1[alkene]-1, vary in the order: vinylferrocene (4800 M-1) ? ethylene (7.0) ≈ α-olefins > cis-2-butene (2.2) > trans-2-butene (a CD2Cl2 molecule, and rapid rotation of the alkene around the metal-(alkene centroid) axis.

Coordination of alkenes and alkynes to a cationic d0 zirconocene alkoxide complex

This paper describes the synthesis of base-free (C5R5)2Zr(OtBu)+ cations, the direct observation of nonchelated alkene and alkyne adducts of these cations, and studies of the thermodynamic and dynamic properties of these novel species. Reaction of Cp2′ZrMe2 (Cp′ = C5H4Me) with tert-butyl alcohol followed by [Ph3C][B(C6F5)4] in benzene yields [ Cp2′Zr(O′Bu) ][B(C6F5)4] (1), which exists as Cp2′Zr(O′Bu)(CIR)+ solvent adducts in C6D5Cl and CD2Cl2 solutions. Addition of ligands L (L = ethylene, propylene, propyne, 2-butyne, CO, phenylacetylene, allene, 1-hexene, cis-2-butene) to 1 in CD2Cl2 at -89 °C results in reversible formation of Cp2′Zr(O′Bu)(L)+ adducts. NMR data for Cp2′Zr(O′Bu)(H2C=CHMe)+ (4) indicate that the propylene coordinates unsymmetrically and is polarized with positive charge buildup at Cint. Equilibrium constants, defined by Keq = [Zr-L][1]-1[L]-1, vary in the order CO > propyne > 2-butyne > phenylacetylene > ethylene > allene > propylene > 1-hexene > cis-2-butene > vinyl chloride. Loss of L from Cp2′Zr(O′Bu)(L)+to give 1 appears to proceed via associative displacement by CD2Cl2 in most cases. Copyright