Steric Effects in the Reductive Coupling of CO by Mixed-Sandwich Uranium(III) Complexes
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https://figshare.com/articles/dataset/Steric_Effects_in_the_Reductive_Coupling_of_CO_by_Mixed_Sandwich_Uranium_III_Complexes/2436358
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资源简介：
The selectivity of the mixed-sandwich U(III) complexes
of the type
[U(η-C8H6{SiiR3-1,4}2)(η-CpR′)]
(R = Me, iPr; R′ = Me4H, Me5, Me4iPr, Me4SiMe3, Me4Et) toward the reductive coupling of CO to form uranium-bound
oxocarbons has been explored. In this context, the new U(III) mixed-sandwich
complexes [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4TMS)], [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4iPr)], [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4Et)], [U(η-C8H6{SiMe3-1,4}2)(η-Cp*)], and [U(η-C8H6{SiMe3-1,4}2)(η-CpMe4TMS)]
have been prepared and structurally characterized. The reactivity
toward CO is dominated by the “global” sterics around
the uranium center, while selectivity for oxocarbon formation is largely
regulated by the steric bulk of the CpR′ ligand.
Accordingly, with excess CO [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4TMS)] and [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4iPr)] show no reactivity, [U(η-C8H6{SiMe3-1,4}2)(η-CpMe4TMS)] is completely
selective for the formation of the ynediolate complex [U(η-C8H6{SiMe3-1,4}2)(η-CpMe4TMS)]2(μ-η1:η1-13C2O2), [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)] affords only the deltate complex [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-η2:η2-C3O3), and [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4H)] gives solely the squarate complex [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4H)]2(μ-η2:η2-C4O4). Additionally,
the squarate moiety has been removed from the uranium center in the
last complex by reaction with Me3SiCl to afford the TMS
ester of squaric acid, C4O2(OTMS)2.
创建时间：
2016-02-19
