The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation

Lu, Jun-Bo1,2; Ma, Xue-Lu1,2,3; Wang, Jia-Qi1,2; Jiang, Ya-Fei1,2; Li, Yong1,2; Hu, Han-Shi1,2; Xiao, Hai1,2; Li, Jun1,2,4

2019-06-03

10.1021/acs.inorgchem.9b00598

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

Single transition-metal site catalysts with s-, p-, or d-block atom anchor for nitrogen fixation have been extensively studied, and yet the studies of the f-block atom anchor are rarely reported. Thus, we investigate the feasibility of using a newly synthesized U-Co complex featuring a single CoI site coordinated by tetrakis(phophinoamide) and an UIV anchor for N-2-to-NH3 conversion by theoretical modeling. We characterize the evolution of oxidation states of U and Co along the reaction pathways from ab initio density matrix renormalization group (DMRG) calculations, and we find that the variation of the Co -> U dative bond is correlated with the changes of oxidation states. Both uranium and cobalt can serve as electron reservoirs to facilitate breaking the N-N bond. Our study demonstrates the viability of metal -> metal dative bonds, particularly the df-d one, for the reduction of N-2 to NH3, and thus, this opens up a new avenue to the rational design of efficient catalyst for nitrogen fixation.

SCI

英语

NI期刊

通讯

Fundamental Research Funds for the Central Universities[2019QH01]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000470332200034

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Tsinghua Univ, Minist Educ, Dept Chem, Beijing 100084, Peoples R China
2.Tsinghua Univ, Minist Educ, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China
3.China Univ Min & Technol, Sch Chem & Environm Engn, Beijing 100083, Peoples R China
4.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Lu, Jun-Bo,Ma, Xue-Lu,Wang, Jia-Qi,et al. The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation[J]. INORGANIC CHEMISTRY,2019,58(11):7433-7439.

Lu, Jun-Bo.,Ma, Xue-Lu.,Wang, Jia-Qi.,Jiang, Ya-Fei.,Li, Yong.,...&Li, Jun.(2019).The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation.INORGANIC CHEMISTRY,58(11),7433-7439.

Lu, Jun-Bo,et al."The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation".INORGANIC CHEMISTRY 58.11(2019):7433-7439.