C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo2Cp2(μ-CPh)(μ-PCy2)(CO)2] with Small Unsaturated Organics

Garcı́a, M. Esther; García‐Vivó, Daniel; Menéndez, Sonia; Ruiz, Miguel A.

doi:10.1021/acs.organomet.6b00552

Cited by 6 publications

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References 61 publications

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“…2 In particular, the intramolecular alkyne insertion into a metal−carbon bond, in di-and trinuclear metal complexes, represents an intriguing strategy to grow various hydrocarbyl fragments stabilized by bridging multisite coordination. 3 However, [Fe 2 Cp 2 (CO) 4 ] is a long time known, easily available and robust compound, 4 previously used as a starting material for pioneering studies to explore new C−C bond coupling reactions and to model the Fischer−Tropsch process. 5 The construction of organometallic motifs supported on the [Fe 2 Cp 2 (CO) x ] skeleton has witnessed a renewed interest, 6 in view of the current huge effort to develop sustainable synthetic routes based on earth abundant metals, 7 and the awareness that nature uses diiron organometallic units to perform amazingly efficient enzymatic processes.…”

Section: ■ Introductionmentioning

confidence: 99%

DFT Mechanistic Insights into the Alkyne Insertion Reaction Affording Diiron μ-Vinyliminium Complexes and New Functionalization Pathways

et al. 2018

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Insertion of propyne or 2-butyne into the Fe-carbyne bond belonging to the fragment [Fe2Cp2(CO)(µ-CO){µ-CNMe(R)}] + (R = Me or Xyl = 2,6-C6H3Me2) was DFT investigated, and plausible intermediates were identified along the formation of the vinyliminium complexes [Fe2Cp2(CO)(µ-CO){µ-η 1 :η 3 -C(Me)C(R′′)CN(Me)(R)}]SO3CF3, [2a-d] + , thus allowing to explain regio-and stereochemical features. The X-ray structure of [2a]SO3CF3 (R = Me, R′′ = H) was determined by single crystal X-ray diffraction. Novel C-C and C-S bond forming pathways involving the vinyliminium ligand were then explored. Thus, [2b]SO3CF3 (R = Xyl, R′′ = H) reacted with cyclopentadiene (or cyclopentene), triphenylphosphonium methylide and benzyl bromide, in tetrahydrofuran in the presence of sodium hydride, to give respectively [Fe2Cp2(CO)(µ-CO){µ-η 1 :η 2 -C(Me)C{C(CH)4}CN(Me)(Xyl)}], 3, [Fe2Cp2(CO)(µ-CO){µ-η 1 :η 2 -C(Me)C(CH2)CN(Me)(Xyl)}], 4, and [Fe2Cp2(CO)(µ-CO){µ-η 1 :η 3 -C(Me)C(CH2Ph)CN(Me)(Xyl)}]Br, [5]Br, in good yields. The unstable complex 4 (detected by IR spectroscopy) readily converted into [2c]SO3CF3 (R = Xyl, R′′ = Me) upon HSO3CF3 protonation of the methylide function. [5]Br was obtained as E/Z isomeric mixture, which was then quantitatively converted into the most stable Z form, by heating in methanol solution at 50 °C. The reactions of [2cd]SO3CF3 (R = Me, Xyl, R′′ = Me) with PhSSPh/NaH selectively yielded the aminoalkylidyne species [Fe2Cp2(SPh)(CO)(µ-CO){µ-CN(Me)(Xyl)}], 6, and the bis-alkylidene [Fe2Cp2(CO)(µ-CO){µ-η 1 :η 2 -C(Me)C(Me)(SPh)CN(Me)2}], 7, respectively, probably via the intermediacy of the radical compounds 2c-d. The structures of 3-7 and 2c-d were elucidated by DFT calculations, and the isolated products were characterized by analytical and spectroscopic methods.

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Section: ■ Introductionmentioning

confidence: 99%

DFT Mechanistic Insights into the Alkyne Insertion Reaction Affording Diiron μ-Vinyliminium Complexes and New Functionalization Pathways

et al. 2018

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“…Recently published dinuclear [(h 5 -C 5 H 5 )Mo] complexes, bridged likewise by an alkylidyne ligand, allowed a reversible addition of CO affording a m-k 1ketenyl ligand (D and E, Chart 1). 36,39,40 Similarly, the coupling reaction of a ketenyl ligand with a phenyl group of a pincer ligand at tungsten is reversible depending on THF coordination (F and G, Chart 1). 41 MI into a W-ketenyl bond has been reported for only a single case employing isocyanate, but the underlying mechanism remained open.…”

Section: Introductionmentioning

confidence: 99%