Ligand effect on the reactivity difference of Mo Tris(dithiolene) complexes towards Ethylene: A computational study

Yang, Ti-Long; Ni, Shao-Fei; Zhang, Pan; Dang, Li

2016-03-15

10.1016/j.jorganchem.2016.01.017

JOURNAL OF ORGANOMETALLIC CHEMISTRY   影响因子和分区

0022-328X

1872-8561

Dithiolene ligand based additions of ethylene with a series of the Mo tris(dithiolene) complexes were studied by using density functional theory (DFT) methods. Computational results show that both the electronic effect and the ligand distortion come from the substituents of unreacted and reacted dithiolene ligands have significant impact on the reactivity of Mo tris(dithiolene) complexes towards ethylene. The complexes with strong electron withdrawing groups, i.e. -CN and -CF3, introduced at the unreacted ligands can increase the reactivity of reacted dithiolene with ethylene. However, keeping a strong electron withdrawing groups on the unreacted ligands, the cyclized conjugated substituents on the reacted ligand of Mo tris(dithiolene) complexes lead to its higher reactivity with ethylene than other complexes, due to the larger ligand distortion coming from the better interaction between the metal d(z2) orbital and the ligand pi bonding orbital. Our study shed new light on the ligand effect on the reactivity of metal dithiolene complexes towards simple olefins such as ethylene. These finding are expected to guide the material design for olefin abstraction. (C) 2016 Elsevier B.V. All rights reserved.

Dithiolene ligand Ethylene addition DFT

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China[21573102]

Chemistry

Chemistry, Inorganic & Nuclear ; Chemistry, Organic

WOS:000370445100008

ELSEVIER SCIENCE SA

20160601892373

Chemical bonds ; Computation theory ; Density functional theory ; Design for testability ; Ethylene

Computer Theory, Includes Formal Logic, Automata Theory, Switching Theory, Programming Theory:721.1 ; Physical Chemistry:801.4 ; Organic Compounds:804.1 ; Probability Theory:922.1

CHEMISTRY

Web of Science

South Univ Sci & Technol China, Dept Chem, Shenzhen 518055, Peoples R China

Yang, Ti-Long,Ni, Shao-Fei,Zhang, Pan,et al. Ligand effect on the reactivity difference of Mo Tris(dithiolene) complexes towards Ethylene: A computational study[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2016,806:60-67.

Yang, Ti-Long,Ni, Shao-Fei,Zhang, Pan,&Dang, Li.(2016).Ligand effect on the reactivity difference of Mo Tris(dithiolene) complexes towards Ethylene: A computational study.JOURNAL OF ORGANOMETALLIC CHEMISTRY,806,60-67.

Yang, Ti-Long,et al."Ligand effect on the reactivity difference of Mo Tris(dithiolene) complexes towards Ethylene: A computational study".JOURNAL OF ORGANOMETALLIC CHEMISTRY 806(2016):60-67.