Alkene Isomerization–Hydroboration Catalyzed by First-Row Transition-Metal (Mn, Fe, Co, and Ni) N-Phosphinoamidinate Complexes: Origin of Reactivity and Selectivity
| Autor: | Michael D. Lumsden, Daniel H. Ess, Laura Turculet, Michael J. Ferguson, Takahiko Ogawa, Steven M. Bischof, Jack T. Fuller, Robert McDonald, Orson L. Sydora, Casper M. Macaulay, Mark Stradiotto, Doo-Hyun Kwon, Samantha J. Gustafson |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Alkene General Chemistry 010402 general chemistry 01 natural sciences Borylation Medicinal chemistry Catalysis 0104 chemical sciences Hydroboration chemistry.chemical_compound Transition metal chemistry Pyridine Reactivity (chemistry) Selectivity Isomerization |
| Zdroj: | ACS Catalysis. 8:9907-9925 |
| ISSN: | 2155-5435 |
| Popis: | We describe the results of our combined experimental and computational investigation of structurally analogous (N-phosphinoamidinate)metal(N(SiMe3)2) precatalysts ((PN)M; M = Mn2+, Fe2+, Co2+, and Ni2+; d5–d8) in the isomerization–hydroboration of 1-octene, cis-4-octene, or trans-4-octene (1a–c) with HBPin. As part of this investigation, the synthesis and crystallographic characterization of diamagnetic (PN)Ni, ((PN)NiH)2, (PN)NiH(L) (L = pyridine or DMAP), and (PN)Ni(NHdipp) (dipp = 2,6-iPr2C6H3) are reported. Divergent catalytic reactivity and selectivity was noted for members of the (PN)M series; (PN)Mn and (PN)Ni afforded poor hydroboration yields, whereas the use of (PN)Fe or (PN)Co afforded high conversion and selectivity for the terminal borylation product, (n-octyl)BPin (2a). DFT calculations involving (PN)M as well as stoichiometric reactivity studies featuring (PN)Ni confirmed that (PN)MH intermediates generated upon reaction of (PN)M with HBPin represent viable catalytic species whereby formati... |
| Databáze: | OpenAIRE |
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