Synthesis, crystal structure and MMCT of new cyanide-bridged complexes cis-M-II(dppm)(2)(CN)(2)((FeX3)-X-III)(2) (M = Ru, Os)

Wang Yong; Song Jinshuai; Ma Xiao; Xue Zhenzhen; Hu Shengmin; Fu Ruibiao; Li Chunsen; Sheng Tianlu; Wu Xintao

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Synthesis, crystal structure and MMCT of new cyanide-bridged complexes cis-M-II(dppm)(2)(CN)(2)((FeX3)-X-III)(2) (M = Ru, Os)

机译：新型氰化物桥络合物CIS-M-II（DPPM）（2）（2）（2）（（FEX3）-X-III）（2）（M = Ru，OS）的合成，晶体结构和MMCT

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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.

机译：两种氰化物前体CIS-M-II（DPPM）（2）（2）（2）（M = Ru，1; OS，2）（DPPM =双（二苯基膦基）的合成，晶体结构，IR和电子吸收光谱分谱甲烷）和四种新的氰化物桥络合物顺式-M-II（DPPM）（2）（2）（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）。晶体结构数据，IR和在电子吸收光谱MMCT（金属对金属的电荷转移）表示沿复合物3-6的Fe-III-NC-M-II阵列一些电子离域的存在。基于基于Ru的复合物（3和4）的较新的MMCT条带的存在应由OS-II的较大的旋转轨道耦合（SoC）产生。此外，晶体结构数据和IR光谱的理论计算值与实验值一致。复合物的温度依赖性磁性3-6揭示了遥远Fe-III离子之间非常弱的金属 - 金属相互作用的存在。

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《RSC Advances》 |2015年第5期|共9页
作者
Wang Yong; Song Jinshuai; Ma Xiao; Xue Zhenzhen; Hu Shengmin; Fu Ruibiao; Li Chunsen; Sheng Tianlu; Wu Xintao;
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Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

Chinese Acad Sci Fujian Inst Res Struct Matter State Key Lab Struct Chem Fuzhou 350002 Peoples R China;

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1. Synthesis, crystal structure and MMCT of new cyanide-bridged complexes cis-M-II(dppm)(2)(CN)(2)((FeX3)-X-III)(2) (M = Ru, Os) [J] . Wang Yong, Song Jinshuai, Ma Xiao, RSC Advances . 2015,第5期

机译：新型氰化物桥络合物CIS-M-II（DPPM）（2）（2）（2）（（FEX3）-X-III）（2）（M = Ru，OS）的合成，晶体结构和MMCT
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3. Syntheses, crystal structures, MMCT and magnetic properties of four one-dimensional cyanide-bridged complexes comprised of M-II-CN-Fe-III (M = Fe, Ru, Os) [J] . Wang Yong, Ma Xiao, Hu Shengmin, Dalton transactions: An international journal of inorganic chemistry . 2014,第46期

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4. Synthesis and Structure of the First Binuclear Fulvalene Ru Complexes having Ru-H [C] . Masanobu Watanabe, Munetaka Akita Symposium on Organometallic Chemistry . 2004

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Synthesis, crystal structure and MMCT of new cyanide-bridged complexes cis-M-II(dppm)(2)(CN)(2)((FeX3)-X-III)(2) (M = Ru, Os)

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