Synthesis, crystal structure and MMCT of new cyanide-bridged complexes cis-MII(dppm)2(CN)2(FeIIIX3)2 (M = Ru, Os)

被引：11

作者：

Wang, Yong ^{[1
,2
]}

Song, Jinshuai ^{[1
]}

Ma, Xiao ^{[1
]}

Xue, Zhenzhen ^{[1
,2
]}

Hu, Shengmin ^{[1
]}

Fu, Ruibiao ^{[1
]}

Li, Chunsen ^{[1
,3
]}

Sheng, Tianlu ^{[1
]}

Wu, Xintao ^{[1
]}

机构：

[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China

[2] Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China

[3] Fujian Prov Key Lab Theoret & Computat Chem, Xiamen 361005, Fujian, Peoples R China

来源：

RSC ADVANCES | 2015年 / 5卷 / 05期

基金：

美国国家科学基金会;

关键词：

CHARGE-TRANSFER IVCT; PHOTOPHYSICAL PROPERTIES; REDUCTION POTENTIALS; CLASS-II; VALENCE; RUTHENIUM; TRANSITION; TRINUCLEAR; DINUCLEAR; ADDUCTS;

D O I：

10.1039/c4ra13825b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The syntheses, crystal structures, IR and electronic absorption spectroscopy of two cyanide precursors cis-M-II(dppm)(2)(CN)(2) (M = Ru, 1; Os, 2) (dppm = bis(diphenylphosphino)methane) and four new cyanide-bridged complexes cis-M-II(dppm)(2)(CN)(2)((FeX3)-X-III)(2) (M = Ru, X = Cl, 3; M = Ru, X = Br, 4; M = Os, X = Cl, 5; M = Os, X = Br, 6) are reported. The crystal structural data, IR and the MMCT (metal-to-metal charge transfer) in the electronic absorption spectroscopy indicate the existence of some electron delocalization along Fe-III-NC-M-II arrays in complexes 3-6. The presence of a newer MMCT band of the Os-based complexes (5 and 6) than the Ru-based complexes (3 and 4) should result from the larger spin-orbit coupling (SOC) of Os-II. Also the theoretical calculated values of the crystal structural data and IR spectra are consistent with the experimental values. Temperature-dependent magnetic properties of complexes 3-6 reveal the presence of the very weak metal-metal interaction between distant Fe-III ions.

引用

页码：3399 / 3407

页数：9

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