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- W2023588093 abstract "Oxidative decarbonylation of (η5-C5R5)Mo(CO)3X and isoelectronic four-legged piano-stool Mo(II) precursors to homogeneous olefin epoxidation catalysts has garnered significant attention as an alternative to organorhenium oxides RReO3. An emerging theme has been the introduction of donor-functionalized cyclopentadienyl ligands to tune catalyst performance. However, the utility of the [2-(diphenylphosphino)ethyl]cyclopentadienyl (CpPPh) ligand under oxidative decarbonylation conditions has not been explored. The application of Mo(VI) and W(VI) compounds containing mono- and bidentate phosphine oxide ligands as epoxidation catalysts suggests that screening MoX(CO)2(η5:η1-CpPPh) as catalyst precursors is a worthy objective. To this end, HM(CO)2(η5:η1-CpPPh) (M = Cr (1), Mo (2), W (3)) were synthesized; the hydrides 1 and 3 are of interest, since 2 is an established precursor for ionic hydrogenation catalysts. Hydrogen–halogen exchange using 1–3 afforded MX(CO)2(η5:η1-CpPPh) (M = Cr, X = I (4); M = Mo, X = Cl (5), Br (6), I (7); M = W, X = Br (8)), while deprotonation of 1–3 provided [K(18C6)][M(CO)2(η5:η1-CpPPh)] (M = Cr (9), Mo (10), W (11)). Complexes 1 and 3–11 have been characterized in solution and by X-ray crystallography. Treatment of 5–7 with t-BuOOH resulted in active cyclooctene and 1-dodecene epoxidation catalysts, with conversion curves and activities similar to those afforded by MoCl(CO)3(η5-C5R5) and MoR(CO)3(η5-C5R5) precursors." @default.
- W2023588093 created "2016-06-24" @default.
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- W2023588093 date "2012-03-15" @default.
- W2023588093 modified "2023-09-28" @default.
- W2023588093 title "Dicarbonyl{[2-(diphenylphosphino)ethyl]cyclopentadienyl} Group VI Metal Hydrides, Halides, and Anions: Precursors for Olefin Epoxidation Catalysts" @default.
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- W2023588093 doi "https://doi.org/10.1021/om300057n" @default.
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