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- W2325215559 abstract "A series of molybdenum(II) and tungsten(II) aldehyde complexes of the type [{Tp{M(CO)(RC⋮CMe)(η1/η2-OCHR‘)][BAr‘4] ({Tp} = Tp‘, Tp; R = Ph, Me) (5−8) has been prepared for the purpose of investigating σ/π-aldehyde binding. The aldehyde complexes were generated by protonation of the methyl complexes {Tp}M(CO)(RC⋮CMe)Me (1−4) with HBAr‘4·OEt2 (HBAr‘4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), loss of methane, and addition of aldehyde (acetaldehyde, propionaldehyde, pivaldehyde, acrolein, trans-crotonaldehyde, methacrolein, benzaldehyde, p-tolualdehyde, or p-anisaldehyde). The aldehyde complexes exhibit varying σ/π-aldehyde coordination depending on the aldehyde, the metal, and the metal's ancillary ligands. Within the series, π-binding is observed only in the electron-rich and sterically less encumbered Tp tungsten complexes (7), where the π/σ-isomer ratio is dependent on the nature of the aldehyde. In contrast, aldehydes are σ-bound in the less electron-rich Tp molybdenum complexes (8) and in the more sterically encumbered Tp‘ tungsten and molybenum complexes 5 and 6. Variable-temperature FTIR measurements show that the π/σ-isomer ratio in the Tp tungsten complexes (7) increases as the temperature is lowered." @default.
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- W2325215559 date "2000-03-18" @default.
- W2325215559 modified "2023-10-09" @default.
- W2325215559 title "Molybdenum and Tungsten η<sup>1</sup>- and η<sup>2</sup>-Aldehyde Complexes" @default.
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- W2325215559 doi "https://doi.org/10.1021/om990864x" @default.
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