Linear trimeric, dimeric, and monomeric titanium(III) aryloxides
- Univ. of Ottawa, Ontario (Canada)
Interest in the chemistry of low-valent titanium has been stimulated by some remarkable performances reported for these systems, including catalytic dinitrogen activation/fixation and the enormous reducing capability of these species with the large majority of organic substances. Reactions of trans-Ti(TMEDA)[sub 2]Cl[sub 2] (TMEDA = N,N,N[prime],N[prime]-tetramethylethylenediamine) with 2 equiv of RONa [R = Ph, 3,5-(t-Bu)[sub 2]C[sub 6]H[sub 3]] formed the paramagnetic light-green linear trimeric Ti(III) derivative Ti[sub 3](PhO)[sub 9]-(TMEDA)[sub 2] (1) and the pink dimeric complex [Ti(RO)Cl(TMEDA)][sub 2]([mu]-OR)[sub 2] [R = 3,5-(t-Bu)[sub 2]C[sub 6]H[sub 3]] (2), respectively. Complex 1 could also be conveniently synthesized from TiCl[sub 3](THF)[sub 3] and PhONa in the presence of TMEDA. Conversely, complex 2 could be obtained from TiCl[sub 3](THF)[sub 3] only when the reaction was carried out in toluene, since bright-yellow crystals of the mononuclear anionic complexes [Ti(RO)[sub 2](TMEDA)Cl[sub 2]][M[prime]] [M[prime] = Na(TMEDA)[sub 2][sup +] (3a), 1/2(TMEDA)H[sup +] (3b)] were isolated when the reaction was performed in THF. Reaction of Ti[N(SiMe[sub 3])[sub 2]][sub 3] with 3 equiv of 2,6-Me[sub 2]C[sub 6]H[sub 3]OH in toluene led to the formation of the first dinuclear homoleptic complex [Ti(RO)[sub 3]][sub 2] [R = 2,6-Me[sub 2]C[sub 6]H[sub 3] (4)], which was isolated as green-blue crystals. A similar reaction with the more bulky 2,6-(i-Pr)[sub 2]C[sub 6]H[sub 3]OH led to the formation of the neutral homoleptic Ti(IV) species Ti[OC[sub 6]H[sub 3]-2,6-(i-Pr)[sub 2]][sub 4] (6). Conversely, the anionic homoleptic complex [Ti[OC[sub 6]H[sub 3]-2,6-(i-Pr)[sub 2]][sub 4]][Li(TMEDA)[sub 2]]-toluene (7) was obtained by reacting the corresponding lithium phenoxide with TiCl[sub 3](THF)[sub 3].
- OSTI ID:
- 7186746
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:24; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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ALKOXIDES
CHEMICAL PREPARATION
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
LATTICE PARAMETERS
NUMERICAL DATA
SCATTERING
SYNTHESIS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION