The role of Si in Ir(SiNN) catalyst and chemoselectivity of dehydrogenative borylation over hydroborylation: A theoretical study

Chen, Shuang1,2; Ni, Shao-Fei3,4,5; Liu, Pei-Nian1,2; Dang, Li3,4,5

2018-12-15

10.1016/j.jorganchem.2018.09.006

JOURNAL OF ORGANOMETALLIC CHEMISTRY   影响因子和分区

0022-328X

1872-8561

An Ir(SiNN) complex has been reported that efficiently catalyzes dehydrogenative C-H borylation, rather than hydroborylation, of terminal alkynes. Here we performed density functional theory calculations to elucidate the reaction mechanism and attempt to explain the strict chemoselectivity for dehydrogenative borylation. The calculations suggest that the chemoselectivity arises mainly from (1) interaction between Si and the metal hydride, which stabilizes the metal center during the addition of HBpin or CH3CCH; and (2) migration of the Bpin onto the amide N of the SiNN pincer ligand, which twists the pincer ligand to provide space for oxidative addition of the terminal alkyne to the Ir center. (c) 2018 Published by Elsevier B.V.

Hydroborylation Dehydrogenative C-H borylation DFT

SCI ; EI

英语

通讯

National Natural Science Foundation of China[21573102]

Chemistry

Chemistry, Inorganic & Nuclear ; Chemistry, Organic

WOS:000449110200007

ELSEVIER SCIENCE SA

20184005905583

Amides ; Density functional theory ; Hydrides ; Hydrocarbons ; Ligands ; Silicon compounds

Physical Chemistry:801.4 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1

CHEMISTRY

Web of Science

1.East China Univ Sci & Technol, Shanghai Key Lab Funct Mat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China
2.East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China
3.Shantou Univ, Dept Chem, Shantou 515063, Guangdong, Peoples R China
4.Shantou Univ, Key Lab Preparat & Applicat Ordered Struct Mat Gu, Shantou 515063, Guangdong, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Chen, Shuang,Ni, Shao-Fei,Liu, Pei-Nian,et al. The role of Si in Ir(SiNN) catalyst and chemoselectivity of dehydrogenative borylation over hydroborylation: A theoretical study[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2018,877:59-67.

Chen, Shuang,Ni, Shao-Fei,Liu, Pei-Nian,&Dang, Li.(2018).The role of Si in Ir(SiNN) catalyst and chemoselectivity of dehydrogenative borylation over hydroborylation: A theoretical study.JOURNAL OF ORGANOMETALLIC CHEMISTRY,877,59-67.

Chen, Shuang,et al."The role of Si in Ir(SiNN) catalyst and chemoselectivity of dehydrogenative borylation over hydroborylation: A theoretical study".JOURNAL OF ORGANOMETALLIC CHEMISTRY 877(2018):59-67.