Density Functional Theory Study of the Reaction between d(0) Tungsten   Alkylidyne Complexes and H2O: Addition versus Hydrolysis

doi:10.1021/acs.inorgchem.7b00713

CORC > 北京大学 > 化学与分子工程学院

	Density Functional Theory Study of the Reaction between d(0) Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis
	Chen, Ping ; Zhang, Linxing ; Xue, Zi-Ling ; Wu, Yun-Dong ; Zhang, Xinhao
刊名	INORGANIC CHEMISTRY
	2017
关键词	INTRAMOLECULAR PROTON-TRANSFER SITE HETEROGENEOUS CATALYSTS OLEFIN METATHESIS CATALYSTS ATOMIC LAYER DEPOSITION OXO PRECATALYSTS IMPACT GAUSSIAN-BASIS SETS X-RAY STRUCTURE ALKYNE METATHESIS MOLECULAR CALCULATIONS CRYSTAL-STRUCTURES
DOI	10.1021/acs.inorgchem.7b00713
英文摘要	The reactions of early-transition-metal complexes with H2O have been investigated: An understanding of these elementary steps,promotes the design of precursors for the preparation of metal oxide materials or supported heterogeneous catalysts. Density functional theory (DFT) calculations have been conducted to investigate two elementary steps of the reactions between tungsten alkylidyne complexes and H2O, i.e., the addition of H2O to the W equivalent to C bond and ligand hydrolysis. Four tungsten:alkylidyne complexes, W(equivalent to CSiMe3)(CH2SiMe3)(3) (A-1), W(equivalent to CSiMe3)((CH2Bu)-Bu-t)(3) (B-1), W(equivalent to(CBu)-Bu-t)((CH2Bu)-Bu-t)(3) (C-1), and W(equivalent to(CBu)-Bu-t)((OBu)-Bu-t)(3) (D-1), have been compared, The DFT studies provide an energy profile, of the two competing pathways. An additional H2O molecule can serve as a proton shuttle, accelerating the H2O addition reaction. The effect of atoms at the a and beta positions has also been examined. Because the lone-pair electrons of an O atom at, the alpha position can interact with the orbital of the proton), the barrier of the ligand-hydrolysis reaction for D-1 is dramatically reduced. Both the electronic and steric effects of the silyl group at the beta position lower the barriers,of both the H2O addition,and ligand-hydrolysis reactions. These new mechanistic findings may lead to the further development of metal complex precursors.; National Natural Science Foundation of China [21232001, 21302006]; MOST of China [2013CB911501]; Shenzhen STIC [KQTD201103, JCYJ20140509093817686]; U.S. National Science Foundation [CHE-1362548, CHE-1633870]; SCI(E); ARTICLE; 12; 7111-7119; 56
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/472758]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Chen, Ping,Zhang, Linxing,Xue, Zi-Ling,et al. Density Functional Theory Study of the Reaction between d(0) Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis[J]. INORGANIC CHEMISTRY,2017.
APA	Chen, Ping,Zhang, Linxing,Xue, Zi-Ling,Wu, Yun-Dong,&Zhang, Xinhao.(2017).Density Functional Theory Study of the Reaction between d(0) Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis.INORGANIC CHEMISTRY.
MLA	Chen, Ping,et al."Density Functional Theory Study of the Reaction between d(0) Tungsten Alkylidyne Complexes and H2O: Addition versus Hydrolysis".INORGANIC CHEMISTRY (2017).