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Rubio-Pérez, Laura; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Passarelli, Vincenzo; Pérez-Torrente, Jesús J; Oro, Luis A
06/2017, Letnik: 8, Številka: 7Journal Article
A well-defined NHC-Ir( iii ) catalyst, Ir(H) 2 (IPr)(py) 3 BF 4 (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene), that provides access to a wide range of aryl- and heteroaryl-silanes by intermolecular dehydrogenative C-H bond silylation has been prepared and fully characterized. The directed and non-directed functionalisation of C-H bonds has been accomplished successfully using an arene as the limiting reagent and a variety of hydrosilanes in excess, including Et 3 SiH, Ph 2 MeSiH, PhMe 2 SiH, Ph 3 SiH and (EtO) 3 SiH. Examples that show unexpected selectivity patterns that stem from the presence of aromatic substituents in hydrosilanes are also presented. The selective bisarylation of bis(hydrosilane)s by directed or non-directed silylation of C-H bonds is also reported herein. Theoretical calculations at the DFT level shed light on the intermediate species in the catalytic cycle and the role played by the ligand system on the Ir( iii )/Ir( i ) mechanism. A well-defined NHC-Ir( iii ) catalyst provides access to a wide range of aryl- and heteroarylsilanes by intermolecular dehydrogenative C-H bond silylation.
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JCR | SNIP | JCR | SNIP | JCR | SNIP | JCR | SNIP |
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