Experimental and Theoretical Study on the Structure and Formation Mechanism of [C6H5Cum]- (m = 1−3)

Autor:	Zichao Tang, Xiao-peng Xing, Ke-Li Han, Shu-tao Sun, Xiao-Jing Liu, Xiang Zhang
Rok vydání:	2007
Předmět:	chemistry.chemical_element Copper Metal chemistry.chemical_compound Crystallography chemistry Insertion reaction Computational chemistry visual_art Atom visual_art.visual_art_medium Molecule Density functional theory Physical and Theoretical Chemistry Sigma bond Ionization energy
Zdroj:	The Journal of Physical Chemistry A. 111:3248-3255
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp066750y
Popis:	The important intermediate phenyl-copper metal complexes [C(6)H(5)Cu(m)]- (m = 1-3), which are produced from the reactions between copper metal clusters formed by laser ablation and the benzene molecules seeded in argon carrier gas, are studied by photoelectron spectroscopy(PES) and density functional theory (DFT). Their structures and bonding patterns are investigated, which results in the conclusion that C(6)H(5) groups bond perpendicularly on copper clusters through Cu-C sigma bond. The formation mechanism of these complexes has been studied at B3LYP//6-311G(d, p)/Lanl2dz level. Direct insertion reaction between [Cu(m)]- and C(6)H(6) yields intermediate complex [C(6)H(5)Cu(m)H]-, and then eliminates the H atom, or releases the H atom to other neutral Cu atoms or anionic Cu ions via H abstraction reaction. The first step is the rate-limiting step with C-H activation and cleavage, and H abstraction by neutral Cu atom is the most energetically favorable pathway for the final step. Moreover, the complex [C(6)H(5)Cu(2)]- is ascertained to be easier to be generated than [C(6)H(5)Cu(3)]- and [C(6)H(5)Cu]-, which are in excellent agreement with the experimental results.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::84408192dbf4c8ae058af1f30b848847 https://doi.org/10.1021/jp066750y Zobrazit plný text záznamu