Synthesis of Titanium Borylimido Compounds Supported by Diamide-Amine Ligands and Their Reactions with Alkynes
| Autor: | Philip Mountford, Benjamin A. Clough |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Organic Chemistry Alkyne chemistry.chemical_element 010402 general chemistry Coupling (probability) 01 natural sciences Medicinal chemistry Amine ligands Cycloaddition 0104 chemical sciences Inorganic Chemistry chemistry Intramolecular force Physical and Theoretical Chemistry Bond cleavage Titanium |
| Zdroj: | Organometallics. 37:3558-3572 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.8b00250 |
| Popis: | We report a combined synthetic, mechanistic, and computational (DFT) study of the synthesis of new diamide-amine-supported titanium borylimides and their reactions with TolCCH and ArFCCH (Tol = 4-C6H4Me, ArF = C6F5). Reaction of Ti{NB(NAr′CH)2}Cl2(py)3 (Ar′ = 2,6-C6H3iPr2) with Li2N2RNMe (N2RNMe = MeN(CH2CH2NR)2) or Li2N2Npy (N2Npy = (2-C5H4N)CMe(CH2NSiMe3)2) afforded the borylimides Ti(N2RNMe){NB(NAr′CH)2}(py) (R = SiMe3 (9), ArF (10), or iPr (11)) and Ti(N2Npy){NB(NAr′CH)2}(py) (21). Compounds 9 and 10 reacted with ArCCH (Ar = Tol or ArF) via [2 + 2] cycloaddition to form the azatitanacyclobutenes Ti(N2RNMe){N{B(NAr′CH)2}C(H)C(Ar)}. In the case of R = ArF these underwent subsequent intramolecular C–F bond cleavage/C–C coupling processes. Reaction of 11 and 21 with TolCCH also formed azatitanacyclobutenes, whereas ArFCCH formed borylamide-acetylides via a C–H bond activation process which is endergonic in the case of TolCCH. On heating, these kinetic products rearranged via alkyne elimination to form the corresponding azatitanacyclobutenes as the thermodynamic outcomes. |
| Databáze: | OpenAIRE |
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