Syntheses of Molybdenum Oxo Alkylidene Complexes through Addition of Water to an Alkylidyne Complex
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Syntheses of Molybdenum Oxo Alkylidene Complexes through Addition of Water to an Alkylidyne Complex.pdf
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Author(s)
Hoveyda, Amir H.
Bukhryakov, Konstantin
Schrock, Richard Royce
Tsay, Charlene
Miller, Peter G
Date Issued
February 2018
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Bukhryakov, Konstantin V., Richard R. Schrock, Amir H. Hoveyda, Charlene Tsay, and Peter Müller. “Syntheses of Molybdenum Oxo Alkylidene Complexes through Addition of Water to an Alkylidyne Complex.” Journal of the American Chemical Society 140, no. 8 (February 16, 2018): 2797–2800.
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Author's final manuscript
Abstract
Addition of one equiv of water to Mo(CAr)[OCMe(CF 3 ) 2 ] 3 (1,2 - dimethoxyethane) ( 2, Ar = o-(OMe)C 6 H 4 ) in the presence of PPhMe 2 leads to formation of Mo(O)(CHAr)[OCMe(CF 3 ) 2 ] 2 (PPhMe 2 ) ( 3(PPhMe 2 ) ) in 3 4 % yield. Addition of one equiv of water alone to 2 produces the dimeric alkylidyne hydroxide complex, { Mo(CAr)[OCMe(CF 3 ) 2 ] 2 ( [mu]-OH)}2(dme) ( 4(dme)) in which each bridging hydroxide proton points toward an oxygen atom in an aryl methoxy group. Addition of PMe 3 to 4(dme) gives the alkylidene oxo complex, (3(PMe 3)), ananalog of 3(PPhMe 2)(95% conversion, 66% isolated). Treatment of 3(PMe 3) with two equiv of HCl gave Mo(O)(CHAr)Cl 2 (PMe 3)(5), which upon addition of LiO-2,6-(2,4,6-i-Pr 3 C 6 H 2) 2C 6 H 3 (LiOHIPT) gave Mo(O)(CHAr)(OHIPT)Cl(PMe 3)(6). Compound 6 in the presence of B(C6F5)3 will initiate the ring - opening metathesis polymeri- zation of cyclooctene, 5,6 - dicarbomethoxynorbornadiene (DCMNBD), and rac-5,6-dicarbomethoxynorbornene (DCMNBE), and the homocouplin g of 1-decene to 9-octa decene. The poly(DCMNBD) has a cis,syndiotactic structure, whereas poly(DCMNBE) has a cis,syndiotactic,alt structure. X - ray structures were obtained for 3(PPhMe 2 ), 4(dme), and 6.
MIT Department
Massachusetts Institute of Technology. Institute for Medical Engineering & Science
Massachusetts Institute of Technology. Department of Biology
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.8b00499
