Activation of propargylic alcohols by dimolybdenum tris(μ-thiolate) complexes: Influence of the substituents R in HCCCR2(OH)-vinylidene/allenylidene transformation. Reactivity of allenylidene complexes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Organometallic Chemistry Année : 2007

Activation of propargylic alcohols by dimolybdenum tris(μ-thiolate) complexes: Influence of the substituents R in HCCCR2(OH)-vinylidene/allenylidene transformation. Reactivity of allenylidene complexes

Résumé

Reaction of the bis(nitrile) complex [Mo2Cp2(μ-SMe)3(NCMe)2](BF4) (1) with dimethylpropargylic alcohol, HCtriple bond; length of mdashCCMe2(OH), at room temperature in dichloromethane produced good yields of the μ-alkynol species [Mo2Cp2(μ-SMe)3{μ-CHCCMe2(OH)}](BF4) (2a) through replacement of the two acetonitrile ligands in 1 by the alkynol. The NMR spectra of 2a indicate a μ-η1:η1 coordination mode for the alkyne which is thereby incorporated into a dimetallacyclobutene ring like that found here by X-ray diffraction (XRD) analysis of the related complex [Mo2Cp2(μ-SMe)3(μ-η1:η1-CHCCO2Me)](BPh4) (2b). When 2a was stirred with Et3N at room temperature in dichloromethane, deprotonation gave high yields of the μ-3-hydroxyalkynyl derivative [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCCMe2(OH)}] (3), together with small amounts of the already-known vinylacetylide [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCC(Me)CH2}] (4) resulting from dehydration of 3. Treatment of 3 with 1 equiv. of HBF4 · OEt2 in diethyl ether at room temperature gave the 3-hydroxyvinylidene derivative [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCHCMe2(OH)}](BF4) (5) as the major product, together with other minor products [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCHC(Me)CH2}](BF4) (6), [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCCMe2)](BF4) (7), [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCH2)](BF4) (8), [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCH(CHMe2)}](BF4) (9) and [Mo2Cp2(μ-SMe)3(μ-O)](BF4) (10). The vinylidene (6) and allenylidene (7) species resulted from dehydration of the 3-hydroxyvinylidene complex 5 whereas the vinylidene derivative 8 was formed by deketonisation of 5. When 3 reacted with a large excess of HBF4 · OEt2 in dichloromethane, the 3-isopropylvinylidene complex 9 was obtained nearly quantatively via a Hradical dot radical process. When left for several days CD2Cl2 solutions of 5 afforded mainly the vinylidene species 8 by deketonisation and the side-oxoproduct [Mo2Cp2(μ-SMe)3(μ-O)](BF4) (10) by hydrolysis or reaction with oxygen. Addition of nucleophiles (H−, OMe−, OH−, SMe−) to the allenylidene complex [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCCPh2)](BF4) (11) resulted in the formation of the corresponding μ-acetylide derivatives [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCCRPh2)] [R = H (12), OMe (16a), OH (17), SMe (16b)], which by further reaction with tetrafluoroboric acid afforded either the vinylidene species [Mo2Cp2(μ-SMe)3{μ-η1:η2-CCH(CRPh2)}](BF4) when R = H (13), or the starting complex 11 when R is a leaving group (OMe). Reaction of 13 with Na(BH4) gave the μ-alkylidyne complex [Mo2Cp2(μ-SMe)3(μ-η1-CCH2CPh2H)] (14) by nucleophilic attack of H− at the Cβ carbon atom of the vinylidene chain. Proton addition at Cα in 14 led to the formation of a μ-vinylidene compound 15 containing an agostic C–H bond. New complexes have been characterised by elemental analyses and spectroscopic methods, supplemented for 2b and 3 by X-ray diffraction studies.

Dates et versions

hal-01581394 , version 1 (04-09-2017)

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Wilfried-Solo Ojo, Jean-François Capon, Alan Le Goff, François Y. Pétillon, Philippe P. Schollhammer, et al.. Activation of propargylic alcohols by dimolybdenum tris(μ-thiolate) complexes: Influence of the substituents R in HCCCR2(OH)-vinylidene/allenylidene transformation. Reactivity of allenylidene complexes. Journal of Organometallic Chemistry, 2007, 692 (24), pp.5351 - 5367. ⟨10.1016/j.jorganchem.2007.08.023⟩. ⟨hal-01581394⟩
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