Carbo, Jorge J. published the artcileConstruction of titanasiloxanes by incorporation of silanols to the metal oxide model [{Ti(η5-C5Me5)(μ-O)}3(μ3-CR)]: DFT elucidation of the reaction mechanism, Product Details of C9H22OSi, the publication is Chemistry – A European Journal (2008), 14(26), 7930-7938, database is CAplus and MEDLINE.
A family of novel titanasiloxanes containing the structural unit {[Ti(η5-C5Me5)O]3} were synthesized by hydron-transfer processes involving reactions with equimol. amounts of μ3-alkylidyne derivatives [{Ti(η5-C5Me5)(μ-O)}3(μ3-CR)] (R = H (1), Me (2)) and monosilanols, R3‘Si(OH), silanediols, R2‘Si(OH)2, and the silanetriol tBuSi(OH)3. Treatment of 1 and 2 with triorganosilanols (R’ = Ph, iPr) in hexane affords the new metallasiloxane derivatives [{Ti(η5-C5Me5)(μ-O)}3(μ-CHR)(OSiR3‘)] (R = H, R’ = Ph (3), iPr (4); R = Me, R’ = Ph (5), iPr (6)). Analogous reactions with silanediols, (R’ = Ph, iPr), give the cyclic titanasiloxanes [{Ti(η5-C5Me5)(μ-O)}3(μ-O2SiR’2)(R)] (R = Me, R’ = Ph (7), iPr (8): R = Et, R’ = Ph (9), iPr (10)). Use of tBuSi(OH)3 with 1 or 2 at room temperature produces the intermediate complexes [{Ti(η5-C5Me5)(μ-O)}3(μ-O2Si(OH)tBu)(R)] (R = Me (11), Et (12)). Further heating of solutions of 11 or 12 affords the same compound with an adamantanoid structure, [{Ti(η5-C5Me5)(μ-O)}3(η-O3SitBu)] (13) and methane or ethane elimination, resp. The x-ray crystal structures of 3, 4, 6, 8, 10, 12, and 13 were determined To gain an insight into the mechanism of these reactions, DFT calculations were performed on the incorporation of monosilanol to the model complex [{Ti(η5-C5H5)(μ-O)}3(μ3-CMe)] (2H). The propose mechanism consists of three steps: (1) hydron transfer from the silanol to one of the O atoms of the Ti3O3 ring, forming a titanasiloxane; (2) intramol. hydron migration to the alkylidyne moiety; and (3) a μ-alkylidene ligand rotation to give the final product.
Chemistry – A European Journal published new progress about 17877-23-5. 17877-23-5 belongs to alcohols-buliding-blocks, auxiliary class Protection and Derivatization Reagent, name is Triisopropylsilanol, and the molecular formula is C9H22OSi, Product Details of C9H22OSi.
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