2022
DOI: 10.1002/anie.202213431
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Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes

Abstract: Silanes are important in chemistry and material science. The self-redistribution of HSiCl 3 is an industrial process to prepare SiH 4 , which is widely used in electronics and automobile industries. However, selective silane cross-redistribution to prepare advanced silanes is challenging. We now report an enthalpy-driven silane cross-redistribution to access bis-silanes that contain two different types of SiÀ H bonds in the same molecule. Compared with entropy-driven reactions, the enthalpy-driven reaction sho… Show more

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Cited by 18 publications
(12 citation statements)
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“…Finally, INT‐5 smoothly undergoes Ni(II)/Ni(0) reductive elimination via TS‐4 , giving product 3 bi while regenerating the Ni(0)‐species INT‐1 . Therefore, compared to the reported C−Si/Si−H bond cross‐exchange that favors acyclic over bis‐silacyclic products, [11] we propose that our catalysis enables the utilization of a unique Si−C( sp 3 ) bond activation mode for constructing large bis‐silacyclic ring systems. These calculations underscore a unique mode of action of the Si−H moiety in stabilizing the metal center during Si−C( sp 3 ) cleavage, which we presume is a key reason underlying the observed precedence of C−Si/C−Si bond cross‐exchange versus the reported C−Si/Si−H bond cross‐exchange.…”
Section: Methodsmentioning
confidence: 80%
See 1 more Smart Citation
“…Finally, INT‐5 smoothly undergoes Ni(II)/Ni(0) reductive elimination via TS‐4 , giving product 3 bi while regenerating the Ni(0)‐species INT‐1 . Therefore, compared to the reported C−Si/Si−H bond cross‐exchange that favors acyclic over bis‐silacyclic products, [11] we propose that our catalysis enables the utilization of a unique Si−C( sp 3 ) bond activation mode for constructing large bis‐silacyclic ring systems. These calculations underscore a unique mode of action of the Si−H moiety in stabilizing the metal center during Si−C( sp 3 ) cleavage, which we presume is a key reason underlying the observed precedence of C−Si/C−Si bond cross‐exchange versus the reported C−Si/Si−H bond cross‐exchange.…”
Section: Methodsmentioning
confidence: 80%
“…Combined, the reaction via TS-3 leads to the formation of Ni(II)-species INT-5, featuring a Ni(II)/ SiÀ H agostic interaction within a nine-membered Ni(II)silacyclic structure, which again underscores the mode of assistance of the SiÀ H moiety that is uniquely observed in the current catalytic system. In fact, despite our searches for Therefore, compared to the reported CÀ Si/SiÀ H bond cross-exchange that favors acyclic over bis-silacyclic products, [11] we propose that our catalysis enables the utilization of a unique SiÀ C-(sp 3 ) bond activation mode for constructing large bissilacyclic ring systems. These calculations underscore a unique mode of action of the SiÀ H moiety in stabilizing the metal center during SiÀ C(sp 3 ) cleavage, which we presume is a key reason underlying the observed precedence of CÀ Si/ CÀ Si bond cross-exchange versus the reported CÀ Si/SiÀ H bond cross-exchange.…”
Section: Methodsmentioning
confidence: 84%
“…Recently, substantial progress has been achieved in the synthesis of arylsilanes through transition metal-catalyzed cross-coupling of aryl electrophiles with silicon reagents, [56][57][58][59] as well as in C-H bond silylation reactions. [60][61][62][63][64][65][66][67][68][69][70][71] These important methods successfully overcome the incompatibility issues associated with traditional approaches employing Grignard and organolithium reagents.…”
Section: Introductionmentioning
confidence: 99%
“…This attention has been directed particularly toward the catalytic cleavage and transformations of silicon–carbon bonds in four-membered silacyclobutanes (SCBs) . The significance lies in the remarkable stability of silicon–carbon bonds, which makes the development of innovative transformations through transition-metal-catalyzed silicon–carbon bond activation an exciting avenue for generating a wide array of new organosilicon compounds . In this context, transition-metal-catalyzed ring expansion of SCBs with alkynes, cyclopropenes, allenoates, aldehydes, or other substrates has been successfully employed to synthesize medium-ring silacycles with outstanding chemical selectivity and stereoselectivity.…”
mentioning
confidence: 99%