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Vanadium(V) hydrazido(2-) thiolate imine alkoxide complexes
Sanjukta Banerjee1, Aaron L Odom
1Michigan State University, Department of Chemistry, East Lansing, MI 48824, USA.
Dalton Transactions (Cambridge, England : 2003)
|April 3, 2008
Summary
New vanadium complexes featuring the TIP ligand were synthesized. X-ray diffraction of a phosphine derivative revealed a short N-N bond, suggesting a significant isodiazene resonance form in vanadium chemistry.
Area of Science:
- Organometallic Chemistry
- Vanadium Complexes
- Coordination Chemistry
Background:
- Vanadium complexes are of interest due to their diverse oxidation states and catalytic applications.
- Ligand design plays a crucial role in stabilizing unusual coordination geometries and electronic structures.
Purpose of the Study:
- To synthesize and characterize novel vanadium complexes incorporating the 2-((2-thiolatophenylimino)methylene)phenolate (TIP) ligand.
- To investigate the structural and electronic properties of these new vanadium compounds.
- To explore the reactivity of vanadium complexes with different anionic and neutral ligands.
Main Methods:
- Synthesis of vanadium complexes via reactions of silylated precursors with vanadium amide and aryloxide starting materials.
- Ligand exchange reactions to introduce iodide, phosphine, and other counterions.
- X-ray diffraction analysis to determine the molecular structure of the phosphine derivative.
Main Results:
- The reaction of (Me(3)Si)(2)TIP with V(NNMe(2))(OAr)(3) yielded V(NNMe(2))(TIP)(OAr).
- Aryloxide displacement by trimethylsilyl iodide (ISiMe(3)) formed an insoluble iodide complex, V(NNMe(2))(TIP)(I).
- The iodide complex served as a precursor for three new complexes: [V(NNMe(2))(TIP)(dmpe)]I, [V(NNMe(2))(TIP)(Bu(t)bpy)][OTf], and [V(NNMe(2))(TIP)(Bu(t)bpy)][SbF(6)].
- X-ray diffraction of [V(NNMe(2))(TIP)(dmpe)]I revealed a short N-N bond distance (1.293(3) Å), indicative of a dominant isodiazene resonance form.
Conclusions:
- Novel vanadium(IV) or vanadium(V) complexes with the TIP ligand have been successfully synthesized.
- The structural characterization of a phosphine derivative provides evidence for significant isodiazene character in the V-N-N moiety.
- These findings contribute to the understanding of bonding and electronic structures in vanadium coordination chemistry.
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