109630-89-9Relevant academic research and scientific papers
Insertion reactions of nitriles in cationic alkylbis(cyclopentadienyl)titanium complexes: The facile synthesis of azaalkenylidene titanium complexes and the crystal and molecular structure of [(indenyl)2Ti(NCMePh)(NCPh)]BPh4
Bochmann, Manfred,Wilson, Ladislav M.,Hursthouse, Michael B.,Motevalli, Majid
, p. 1148 - 1154 (2008/10/08)
The cationic methylbis(cyclopentadienyl)titanium nitrile complexes [Cp2TiMe(N≡CR)]BPh4 (R = Me, n-Pr, t-Bu, Ph) are readily converted to the azaalkenylidene complexes [Cp2Ti(N=CMeR)(NCR)]BPh4 as the products of a migratory insertion of nitriles into the Ti-methyl bond. The kinetics of the insertion reactions show a first-order dependence on the titanium alkyl and zero-order in the concentration of free nitrile. The reaction rates increase in the order Me ? t-Bu 2-iminoacyl complex [Cp2Ti(Me3SiN=CMe)(C=NSiMe3)]BPh4. Bis-(indenyl) complexes are more reactive than their cyclopentadienyl analogues, with reaction rates increasing for R = t-Bu 2TiCl2/ AlR3-catalyzed polymerization of ethylene is discussed. The structure of the complex [(C9H7)2Ti-(NCMePh)(NCPh)]BPh4 was determined by X-ray crystallography. The complex crystallizes in the triclinic system, space group P1, with a = 9.713 (1) A?, b = 11.143 (2) A?, c = 11.363 (2) A?, a = 102.63 (1)°, α = 109.57 (1)°, γ = 80.91°, Z = 1, and Dcalcd = 1.21 g cm-3. The Ti-azavinylidene arrangement is linear with a short Ti-N double bond (1.851 A?); the Me and Ph substituents adopt a Me-outside conformation in the plane bisecting the indenyl-Ti-indenyl angle.
Synthesis and Insertion Reactions of Cationic Alkylbis(cyclopentadienyl)titanium Complexes
Bochmann, Manfred,Wilson, Ladislav M.
, p. 1610 - 1611 (2007/10/02)
The electrophilic 14-electron alkyltitanium cations (+) (cp = η5-cyclopentadienyl) and (+) (ind = η5-indenyl), accessible via several routes, form stable complexes (+) and (+), L = NH3, PMe
