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A dimeric constrained-geometry titanium complex linked by double Ti-CH2-Al-CH2 heterocycles.

Khalil A Abboud1, Peter N Nickias, Eugene Y-X Chen

  • 1Department of Chemistry, University of Florida, PO Box 117200, Gainesville, Florida 32611-7200, USA. abboud@ufl.edu

Acta Crystallographica. Section C, Crystal Structure Communications
|January 10, 2002
PubMed
Summary

This study details the crystal structure of a titanium-aluminum complex, revealing unique bridging heterocycles and alpha-agostic interactions that stabilize electron-deficient titanium centers.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Titanium complexes are crucial in catalysis and materials science.
  • Understanding the structural nuances of titanium-aluminum heterocycles is key to developing new applications.
  • Stabilization of electron-deficient metal centers is a significant challenge in organometallic chemistry.

Purpose of the Study:

  • To elucidate the precise three-dimensional structure of a novel bis(titanium) complex.
  • To investigate the bonding interactions and stabilization mechanisms within this unique heterocycle.
  • To provide a detailed structural basis for future research on titanium-aluminum chemistry.

Main Methods:

  • Single-crystal X-ray diffraction analysis was employed to determine the molecular structure.

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  • The crystal structure was solved and refined to high accuracy.
  • Detailed analysis of bond lengths, angles, and coordination environments was performed.

    • Main Results:

    • The crystal structure of bis([N-[dimethyl(1eta5-2,3,4,6-tetramethylindenyl)silyl]cyclohexylamido-1kappaN](methyl-3kappaC)-di-mu3-methylene-1:2:3kappa3C;1:3:3'kappa3C-tris(pentafluorophenyl-2kappaC)titanium) benzene disolvate, [Me2Si(eta5-2,3,4,6-Me4C9H2)(C6H11N)]Ti[(mu3-CH2)Al(C6F5)3][AlMe(mu3-CH2)]2 or [Ti2(C21H7AlF15)2(C21H31NSi)2].2C6D6, was successfully determined.
    • The dimer resides on an inversion center, with two titanium centers bridged by complex Ti(mu3-CH2)Al(C6F5)3AlMe(mu3-CH2) heterocycles.
    • Two alpha-agostic interactions between titanium and bridging methylene hydrogen atoms were identified, stabilizing the electron-deficient titanium centers.

    Conclusions:

    • The determined structure highlights a novel mode of titanium-aluminum heterocycle formation.
    • Alpha-agostic interactions play a critical role in stabilizing electron-deficient titanium centers in this complex.
    • This structural insight contributes to the fundamental understanding of organometallic bonding and reactivity.