Synthesis of Molybdenum(VI) Neopentylidene Neopentylidyne Complexes
Author(s)Tafazolian, Hosein; Schrock, Richard Royce; Mueller, Peter
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Mo(C-t-Bu)(CH-t-Bu)(Cl)(PMe₂Ph)₂ (1) was prepared as off-white crystals in 26% yield through addition of 2.5 equiv of Mg(CH₂-t-Bu)₂ to Mo(O)[OC(CF₃)₃]₄ in diethyl ether followed by 3 equiv of PMe₂Ph and a workup that includes dichloromethane (the source of Cl). Compound 1 is largely a syn isomer initially that equilibrates to give approximately a 1:1 mixture of syn and anti isomers within 1-2 h. Compound 1 reacts with Li(3,5-dimethylpyrrolide) to give Mo(C-t-Bu)(CH-t-Bu)(η¹-Me₂Pyr)(PMe₂Ph)₂ (2a) as a pale yellow solid in 76% yield, and 2a reacts with Ph3SiOH to give a mixture of syn and anti Mo(C-t-Bu)(CH-t-Bu)(OSiPh3)(PMe₂Ph)₂ (3a) in 84% yield. All three compounds tend to lose PMe2Ph to give 14e monophosphine complexes with the formulas Mo(C-t-Bu)(CH-t-Bu)(X)(PMe₂Ph) (X = Cl, Me₂Pyr, or OSiPh₃), none of which could be isolated. X-ray studies show the structures of 1, 2a, and 3a to be analogous with τ values of 0.45, 0.53, and 0.69, respectively.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
American Chemical Society (ACS)
Tafazolian, Hosein et al. "Synthesis of Molybdenum(VI) Neopentylidene Neopentylidyne Complexes." Organometallics 38, 15 (July 2019): 2888-2891 © 2019 American Chemical Society
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