Synthesis of Tungsten Oxo Alkylidene Complexes
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Schrock_Synthesis of tungsten.pdf
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Author(s)
Peryshkov, Dmitry
Schrock, Richard Royce
Date Issued
October 2012
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Peryshkov, Dmitry V., and Richard R. Schrock. “Synthesis of Tungsten Oxo Alkylidene Complexes.” Organometallics 31, no. 20 (October 22, 2012): 7278-7286.
Version
Author's final manuscript
Abstract
Reaction of W(O)[subscript 2](CH[subscript 2]-t-Bu)[subscript 2](bipy) with a mixture of ZnCl[subscript 2](dioxane), PMe[subscript 2]Ph, and trimethylsilyl chloride in toluene at 100 °C produced the known tungsten oxo alkylidene complex W(O)(CH-t-Bu)Cl[subscript 2](PMe[subscript 2]Ph)[subscript 2] (1a) in 45% isolated yield. The neophylidene analogue W(O)(CHCMe[subscript 2]Ph)Cl[subscript 2](PMe[subscript 2]Ph)[subscript 2] was prepared similarly in 39% yield. The reaction between 1a and LiOR (LiOR = LiOHIPT, LiOHMT) in benzene at 22 °C led to formation of the off-white W(O)(CH-t-Bu)Cl(OR)(PMe[subscript 2]Ph) complexes 4a (OR = OHMT = 2,6-dimesitylphenoxide) and 4b (OR = OHIPT = 2,6-(2,4,6-triisopropylphenyl)[subscript 2]phenoxide). Compound 4a serves as a starting material for the synthesis of W(O)(CH-t-Bu)(OHMT)(2,6-diphenylpyrrolide) (6), W(O)(CH-t-Bu)[N(C[subscript 6]F[subscript 5])[subscript 2]](OHMT)(PMe[subscript 2]Ph) (7), W(O)(CH-t-Bu)[OSi(t-Bu)[subscript 3]](OHMT) (8), and W(O)(CH-t-Bu)(OHMT)[subscript 2] (10). The reaction between 8 and ethylene was found to yield the square-pyramidal metallacyclobutane complex W(O)(C[subscript 3]H[subscript 6])[OSi(t-Bu)[subscript 3]](OHMT) (9), while the reaction between 10 and ethylene was found to yield the square-pyramidal metallacyclobutane complex W(O)(C[subscript 3]H[subscript 6])(OHMT)[subscript 2] (11). Compound 11 loses ethylene to yield isolable W(O)(CH[subscript 2])(OHMT)[subscript 2] (12). X-ray structures were determined for 6, 7, 9, and 12.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/om3008579
