Reactivity of the Phosphinidene-Bridged Complexes [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(η6-1,3,5-C6H3tBu3)(CO)2] and [Mo2Cp2(μ-PH)(η6-1,3,5-C6H3tBu3)(CO)2] toward Alkynes: Multicomponent Reactions in the Presence of Ligands
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https://figshare.com/articles/dataset/Reactivity_of_the_Phosphinidene_Bridged_Complexes_Mo_sub_2_sub_Cp_sup_1_sup_sup_1_sup_sup_5_sup_PC_sub_5_sub_H_sub_4_sub_sup_6_sup_1_3_5_C_sub_6_sub_H_sub_3_sub_sup_i_t_i_sup_Bu_sub_3_sub_CO_sub_2_sub_and_Mo_sub_2_sub_Cp_sub_2_sub_PH_sup_6_sup_1_3_5_C_sub/2532925
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The cyclopentadienylidene-phosphinidene complex [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(η6-HMes*)(CO)2] (1) (Cp = η5-C5H5; Mes* = 2,4,6-C6H2tBu3) reacted with RCCR′ in refluxing toluene solutions to give the corresponding phosphide derivatives [Mo2Cp{μ-κ1,η5:κ1,η1-(C5H4)PCRCR′}(η6-HMes*)(CO)2] (R = R′ = CO2Me; R = H, R′ = CO2Me, p-tol), displaying a phosphametallacyclobutene ring. In contrast, the phosphinidene complex [Mo2Cp2(μ-PH)(η6-HMes*)(CO)2] (2) reacted with MeO2CCCCO2Me at room temperature to give first the monocarbonyl phosphide-acyl complex [Mo2Cp2{μ-κ1:κ1,η3-PHC(CO2Me)C(CO2Me)C(O)}(η6-HMes*)(CO)], the latter evolving progressively to the isomeric dicarbonyl [Mo2Cp2(μ-κ1:κ1,η1-PHC(CO2Me)C(CO2Me)}(η6-HMes*)(CO)2] (Mo–P ca. 2.57 Å). When different ligands such as CO, PMe3, P(OMe)3, or CNXyl were added at room temperature to toluene solutions containing compound 1 and different alkynes, relatively fast multicomponent reactions took place to give with good yields the corresponding phosphide-acyl complexes [Mo2Cp{μ-κ1,η5:κ1,η1-(C5H4)PCRCR′C(O)}(η6-HMes*)(CO)2] (R = R′ = CO2Me; R = H, R′ = CO2Me, p-tol), and [Mo2Cp{μ-κ1,η5:κ1,η1-(C5H4)PC(CO2Me)C(CO2Me)C(O)}(η6-HMes*)(CO)(L)] (L = PMe3, P(OMe)3) or the related phosphide-iminoacyl derivatives [Mo2Cp{μ-κ1,η5:κ1,η1-(C5H4)PCRCR′C(NXyl)}(η6-HMes*)(CO)2] (Xyl = 2,6-C6H3Me2; R = R′ = CO2Me; R = H, R′ = CO2Me, C(O)Me), respectively, all of them displaying five-membered phosphametallacyclopentenone or phosphametallacyclopentenimine rings. Separate experiments revealed that the latter complexes (R = R′ = CO2Me) could be decarbonylated photochemically to yield the corresponding monocarbonyls [Mo2Cp{μ-κ1,η5:κ1,η3-(C5H4)PC(CO2Me)C(CO2Me)C(X)}(η6-HMes*)(CO)] (X = O, NXyl), the latter rearranging at room temperature to give the corresponding phosphametallacyclobutene isomers [Mo2Cp{μ-κ1,η5:κ1,η1-(C5H4)PC(CO2Me)C(CO2Me)}(η6-HMes*)(CO)(CX)]. A side product was also formed during the photochemical treatment of the dicarbonyl substrate, it being finally isolated after chromatographic workup as the alkenylphosphide-chloride complex [Mo2CpCl{μ-κ1,η5:κ1,η2-(C5H4)PC(CO2Me)CH(CO2Me)}(η6-HMes*)(CO)] (Mo–P = 2.553(2) and 2.436(2) Ǻ).
创建时间：
2016-02-21
