Electronic and bonding properties of mono-ruthenium-substituted Keggin-type polyoxometalates: a theoretical study of [{PW11O39}RuII/III(L)]n- (L = dimethyl sulfoxide (DMSO), water, pyridine, and ammonia) and [{GeW11O39}RuII(DMSO)3(H2O)]6-

被引：4
|
作者：
Liu, Chun-Guang [1 ,2 ]
Guan, Xiao-Hui [1 ]
机构：
[1] Northeast Dianli Univ, Coll Chem Engn, Jilin, Peoples R China
[2] NE Normal Univ, Fac Chem, Inst Funct Mat Chem, Changchun, Peoples R China
来源：
MOLECULAR PHYSICS | 2013年 / 111卷 / 24期
关键词：
polyoxometalates; density functional theory; electronic structure; bonding properties; ruthenium derivative; EFFECTIVE CORE POTENTIALS; MANGANESE-CONTAINING POLYOXOMETALATE; AB-INITIO; MOLECULAR CALCULATIONS; MAGNETIC-PROPERTIES; CORRELATION-ENERGY; DFT; CATALYST; HYDROXYLATION; EPOXIDATION;
D O I：
10.1080/00268976.2013.785610
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The electronic structure and bonding feature of a series of mono-ruthenium-substituted Keggin-type polyoxometalates (POMs) have been investigated by using density functional theory (DFT) calculation, natural bond orbital (NBO) analysis and energy-decomposition analysis (EDA). A comparison of the electronic properties of two known dimethyl sulfoxide (DMSO)-supported mono-ruthenium-substituted Keggin-type POMs shows that both complexes have the analogous frontier-molecular orbital feature. One of them possesses a relatively small HOMO-LUMO gap because of the high HOMO energy level. This difference comes from a high composition of POM ligand with antibonding feature in HOMO. In addition, three typical Keggin-type POM complexes [{PW11O39}Ru-II/III(L)](n-) (L = H2O, C5H5N, NH3) have also been explored according to our computational studies. The NBO analysis shows that the Ru-II/III-L bond comes from donor-acceptor interactions between the end ligand and the ruthenium (II/III) centre. The EDA shows that the POM complex [{PW11O39}Ru-II(C5H5N)](5-) has much stronger Ru-II-L bond than ammonia-supported Keggin-type POM [{PW11O39}Ru-II(NH3)](5-). And the enhancement of the Ru-II-L bonding interaction in [{PW11O39}Ru-II(C5H5N)](5-) is mainly due to the large orbital interaction energy E-orb. The ammonia-supported Keggin-type POM [{PW11O39}Ru-II(NH3)](5-) and the aqua-ruthenium derivative [{PW11O39}Ru-II(H2O)](5-) have an analogous magnitude of the total bond energy. This result supports a non-aqueous environment for synthesis of an ammonia-supported Keggin-type POM [{PW11O39}Ru-II(NH3)](5-).
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页码：3733 / 3740
页数：8
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