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• W3037488102 endingPage "9682" @default.
• W3037488102 startingPage "9667" @default.
• W3037488102 abstract "In this work, a density functional theory (DFT) study was performed to identify the catalytically active species in the copper-catalyzed three-component reductive hydroxymethylation of styrene with CO2 and hydrosilane. The calculations reveal that the dimeric copper(I) hydride species, formed in a mixture of the bisphosphine ligand, Cu(OAc)2, and hydrosilane, probably acts as the catalyst precursor. In the beginning, this species is catalytically competent to trigger the hydrocupration of styrene, along with the formation of the dimeric copper(I) alkyl intermediate. Subsequently, CO2 insertion into the dimeric copper(I) alkyl intermediate occurs, which is accompanied by the cleavage of the Cu–Cu bond and the generation of the monomeric copper(I) carboxylate intermediate. In the end, the sequential reduction of the monomeric copper(I) carboxylate intermediate with the hydrosilane produces the monomeric copper(I) hydride species as the actual catalyst and turns on the catalytic cycle. On the other hand, the monomeric copper(II) hydride species, yielded as the kinetic product in the initial reaction of the bisphosphine ligand, Cu(OAc)2, and hydrosilane, is also reactive for the hydrocupration of styrene. However, the resulting monomeric copper(II) alkyl intermediate is found to be the catalyst resting state, because of the much higher energy barrier demanded for the subsequent nucleophilic attack toward CO2. On the basis of the results of an activation-strain model (ASM) analysis and charge decomposition analysis (CDA), the low activity of the monomeric copper(II) alkyl intermediate can be ascribed to the more crowded environment around the central copper(II) ion and the weaker nucleophilicity of the alkyl moiety. Furthermore, all of the possible CuH species generated in the system are competent to promote the two-component hydrosilylation of CO2 with hydrosilane, which is an inevitable side reaction along with the reductive hydroxymethylation of styrene with CO2 and hydrosilane." @default.
• W3037488102 created "2020-07-02" @default.
• W3037488102 creator A5008606296 @default.
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• W3037488102 creator A5086879459 @default.
• W3037488102 date "2020-06-25" @default.
• W3037488102 modified "2023-10-16" @default.
• W3037488102 title "Theoretical Characterization of Catalytically Active Species in Reductive Hydroxymethylation of Styrene with CO₂ over a Bisphosphine-Ligated Copper Complex" @default.
• W3037488102 cites W1956738977 @default.
• W3037488102 cites W1982629213 @default.
• W3037488102 cites W1985360331 @default.
• W3037488102 cites W1992173555 @default.
• W3037488102 cites W1993383767 @default.
• W3037488102 cites W1995825925 @default.
• W3037488102 cites W1997551594 @default.
• W3037488102 cites W2001837298 @default.
• W3037488102 cites W2002194503 @default.
• W3037488102 cites W2003699803 @default.
• W3037488102 cites W2008708918 @default.
• W3037488102 cites W2009458392 @default.
• W3037488102 cites W2011215428 @default.
• W3037488102 cites W2011241123 @default.
• W3037488102 cites W2019350573 @default.
• W3037488102 cites W2023246165 @default.
• W3037488102 cites W2023902342 @default.
• W3037488102 cites W2033365705 @default.
• W3037488102 cites W2038767330 @default.
• W3037488102 cites W2042894184 @default.
• W3037488102 cites W2046412723 @default.
• W3037488102 cites W2050838685 @default.
• W3037488102 cites W2051682290 @default.
• W3037488102 cites W2055453175 @default.
• W3037488102 cites W2058363175 @default.
• W3037488102 cites W2060161221 @default.
• W3037488102 cites W2064535886 @default.
• W3037488102 cites W2071295556 @default.
• W3037488102 cites W2073795257 @default.
• W3037488102 cites W2083469020 @default.
• W3037488102 cites W2085336624 @default.
• W3037488102 cites W2085837863 @default.
• W3037488102 cites W2086697252 @default.
• W3037488102 cites W2089759714 @default.
• W3037488102 cites W2091439890 @default.
• W3037488102 cites W2093823059 @default.
• W3037488102 cites W2097595210 @default.
• W3037488102 cites W2104433834 @default.
• W3037488102 cites W2106715828 @default.
• W3037488102 cites W2107458982 @default.
• W3037488102 cites W2120436453 @default.
• W3037488102 cites W2132525235 @default.
• W3037488102 cites W2132673906 @default.
• W3037488102 cites W2133470200 @default.
• W3037488102 cites W2149417324 @default.
• W3037488102 cites W2150697053 @default.
• W3037488102 cites W2163768766 @default.
• W3037488102 cites W2175348449 @default.
• W3037488102 cites W2282200508 @default.
• W3037488102 cites W2310317481 @default.
• W3037488102 cites W2312500145 @default.
• W3037488102 cites W2315869762 @default.
• W3037488102 cites W2319534265 @default.
• W3037488102 cites W2334321457 @default.
• W3037488102 cites W2339206657 @default.
• W3037488102 cites W2345668401 @default.
• W3037488102 cites W2345794494 @default.
• W3037488102 cites W2415237783 @default.
• W3037488102 cites W2432348959 @default.
• W3037488102 cites W2518156262 @default.
• W3037488102 cites W2554346790 @default.
• W3037488102 cites W2557881903 @default.
• W3037488102 cites W2586414578 @default.
• W3037488102 cites W2591342535 @default.
• W3037488102 cites W2597966662 @default.
• W3037488102 cites W2742183380 @default.
• W3037488102 cites W2757945561 @default.
• W3037488102 cites W2762982766 @default.
• W3037488102 cites W2767628767 @default.
• W3037488102 cites W2768093712 @default.
• W3037488102 cites W2771222095 @default.
• W3037488102 cites W2805727788 @default.
• W3037488102 cites W2885802382 @default.
• W3037488102 cites W2890959022 @default.
• W3037488102 cites W2894848096 @default.
• W3037488102 cites W2902476412 @default.
• W3037488102 cites W2902903972 @default.
• W3037488102 cites W2908105707 @default.
• W3037488102 cites W2935344334 @default.
• W3037488102 cites W2950135907 @default.
• W3037488102 cites W2950595271 @default.
• W3037488102 cites W2962812409 @default.
• W3037488102 cites W2974868583 @default.
• W3037488102 cites W2978857893 @default.
• W3037488102 cites W2981127083 @default.

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