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	Syntheses, characterization, redox proper-ties, and mixed-valence chemistry of tetra- and hexanuclear diyndiyl complexes
	Gao, LB; Zhang, LY; Shi, LX; Chen, ZN
刊名	Organometallics
	2005-03-28
卷号	24期号:7页码:1678-1684
ISSN号	0276-7333
DOI	10.1021/om049086l
通讯作者	Chen, zn()
英文摘要	A series of (ru2fe2ii)-fe-ii heterotetranuclear sigma-acetylide complexes [{cp(dppf)ru}(2)(c=c-r-c&3bond; c) (dppf = 1,1'-bis(diphenylphosphino)ferrocene, r = 0, 1; 1,4-benzenediyl, 2; 1,4-naphthalenediyl, 3; 9,10-anthracenediyl, 4) were prepared and characterized by elemental analyses, es-ms spectrometry, ir, h-1 and p-31 nmr, and uv-vis-nir spectroscopy, and cyclic and differential pulse voltammetry. reaction of 1 with [cu(mecn)(4)](clo4) gave ru-2(ii)-fe-2(ii) cu-2(i) heterohexanuclear compound [{cp(dppf)ru}(2){cu(mecn)}(2)(c&3bond; c-c&3bond; c)](clo4)(2) [5(clo4)(2)] through pi-bonding of the acetylides to cu-i centers. the structures of 1 and 5(clo4)-(sbf6) were determined by x-ray crystallography. chemical oxidation of 1, 3, and 4 with an equivalent of ferrocenium. hexafluorophosphate gave one-electron-oxidized species [{cp(dppf)-ru}(2)(c&3bond; c-r-c&3bond; c)](pf6) [r = 0, 1a(pf6); 1,4-naphthalenediyl, 3a(pf6); 9,10-anthracenediyl, 4a(pf6)] with ru-2(ii,iii) mixed valence. electrochemical and visible-infrared spectral studies revealed that the electronic delocalization depends on the r substituent in the bridging ligand c&3bond; c-r-c&3bond; c. while the mixed-valence compound la(pf6) (r = 0) displays an electronically delocalized behavior (class iii mixed-valence system), 3a(pf6) (r = 1,4-naphthalenediyl) and 4a(pf6) (r = 9, 10-anthracenediyl) may belong to borderline compounds between electronic localization and delocalization.
WOS关键词	BIMETALLIC RUTHENIUM COMPLEXES ; DINUCLEAR RHODIUM COMPLEXES ; CARBON-CHAIN COMPLEXES ; ELECTRONIC DELOCALIZATION ; METAL-COMPLEXES ; ACETYLIDE COMPLEXES ; C2RHC4RHC2 CHAIN ; OXIDATION-STATES ; FP-ASTERISK ; POLYYNEDIYL
WOS研究方向	Chemistry
WOS类目	Chemistry, Inorganic & Nuclear ; Chemistry, Organic
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000227861100040
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2377205
专题	中国科学院大学
通讯作者	Chen, ZN
作者单位	1.Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China 2.Chinese Acad Sci, Grad Sch, Fuzhou 350002, Fujian, Peoples R China 3.Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organomet Chem, Shanghai 200032, Peoples R China
推荐引用方式 GB/T 7714	Gao, LB,Zhang, LY,Shi, LX,et al. Syntheses, characterization, redox proper-ties, and mixed-valence chemistry of tetra- and hexanuclear diyndiyl complexes[J]. Organometallics,2005,24(7):1678-1684.
APA	Gao, LB,Zhang, LY,Shi, LX,&Chen, ZN.(2005).Syntheses, characterization, redox proper-ties, and mixed-valence chemistry of tetra- and hexanuclear diyndiyl complexes.Organometallics,24(7),1678-1684.
MLA	Gao, LB,et al."Syntheses, characterization, redox proper-ties, and mixed-valence chemistry of tetra- and hexanuclear diyndiyl complexes".Organometallics 24.7(2005):1678-1684.

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