ISSN:
0009-2940
Keywords:
Titanium amido complexes
;
Tripodal ligands
;
Ligand dynamics
;
μ2-Imido complex
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A new class of amido titanium(IV) halides containing tripodal ligands H3CC(CH2NR)3TiX (R = Me, X = Cl: 1; R = Me3Si, X = Cl: 2a, Br: 2b; R = SiMe2tBu, X = Cl: 3a, Br: 3b) has been synthesised. Compound 1 has been structurally characterised by X-ray crystallography and found to be dimeric in the crystal displaying an idealised C2 symmetry with bridging amido functions linking the two halves of the molecule. The dimeric structure is retained in solution as has been shown by 1H- and 13C-NMR spectroscopy which has also revealed a high degree of ligand dynamics, effecting the interconversion of the two enantiomeric forms of the molecule. This process has been investigated by variable temperature NMR studies and phase-sensitive 1H-NOESY/EXSY spectra. The dimeric μ-imido complexes [H3CC(CH2NSiMe3)2 (H)CH2NTiX]2 (X = Cl: 4a, Br: 4b) have been isolated as a byproduct in the synthesis of 2a/b, and a single-crystal X-ray structure analysis of 4a has established its molecular structure.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260807
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