Remote substituent effects on gas-phase homolytic Fe-O and Fe-S bond energies of p-G-C6H4OFe(CO)2(5-C5H5) and p-G-C6H4SFe(CO)2(5-C5H5) studied using Hartree-Fock and density functional theory methods

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	Remote substituent effects on gas-phase homolytic Fe-O and Fe-S bond energies of p-G-C6H4OFe(CO)2(5-C5H5) and p-G-C6H4SFe(CO)2(5-C5H5) studied using Hartree-Fock and density functional theory methods
	Zeng, Qing ; Li, Zucheng ; Dong, Ling ; Han, Daxiong ; Wang, Rufeng ; Li, Xiangri ; Bai, Genben ; Han DX(韩大雄)
刊名	http://dx.doi.org/10.1002/poc.3152
	2013
关键词	DISSOCIATION-ENERGIES C-H ORGANOMETALLIC COMPOUNDS SPIN-DELOCALIZATION THIOLATE COMPLEXES PHENOXYL RADICALS BINDING-ENERGIES METAL-LIGAND N-H PARASUBSTITUTED PHENOLS
英文摘要	Major State Basic Research Development Program [G2000078100]; Ministry of Science and Technology of China; State Key Laboratory of Elemento-organic Chemistry, Nankai University [201007]; Natural Science Foundation of China [51072093, 91022010]; Metal-ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe-O and Fe-S homolytic bond dissociation energies [Hhomo(Fe-O)'s and Hhomo(Fe-S)'s] of two series of para-substituted phenoxydicarbonyl(5-cyclopentadienyl) iron [p-G-C6H4OFp (1)] and (para-substituted benzenethiolato)dicarbonyl(5-cyclopentadienyl) iron [p-G-C6H4SFp (2)] were studied using Hartree-Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is (5-C5H5)Fe(CO)2, and G are NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO, and NMe2. The results show that DFT methods can provide the best price/performance ratio and accurate predictions of Hhomo(Fe-O)'s and Hhomo(Fe-S)'s. The remote substituent effects on Hhomo(Fe-O)'s and Hhomo(Fe-S)'s [Hhomo(Fe-O)'s and Hhomo(Fe-S)'s] can also be satisfactorily predicted. The good correlations [r=0.98 (g, 1), 0.98 (g, 2)] of Hhomo(Fe-O)'s and Hhomo(Fe-S)'s in series 1 and 2 with the substituent sigma p+ constants imply that the para-substituent effects on Hhomo(Fe-O)'s and Hhomo(Fe-S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. Hhomo(Fe-O)'s (1) and Hhomo(Fe-S)'s (2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright (c) 2013 John Wiley & Sons, Ltd.
语种	英语
出版者	WILEY-BLACKWELL
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/93508]
专题	医学院－已发表论文
推荐引用方式 GB/T 7714	Zeng, Qing,Li, Zucheng,Dong, Ling,et al. Remote substituent effects on gas-phase homolytic Fe-O and Fe-S bond energies of p-G-C6H4OFe(CO)2(5-C5H5) and p-G-C6H4SFe(CO)2(5-C5H5) studied using Hartree-Fock and density functional theory methods[J]. http://dx.doi.org/10.1002/poc.3152,2013.
APA	Zeng, Qing.,Li, Zucheng.,Dong, Ling.,Han, Daxiong.,Wang, Rufeng.,...&韩大雄.(2013).Remote substituent effects on gas-phase homolytic Fe-O and Fe-S bond energies of p-G-C6H4OFe(CO)2(5-C5H5) and p-G-C6H4SFe(CO)2(5-C5H5) studied using Hartree-Fock and density functional theory methods.http://dx.doi.org/10.1002/poc.3152.
MLA	Zeng, Qing,et al."Remote substituent effects on gas-phase homolytic Fe-O and Fe-S bond energies of p-G-C6H4OFe(CO)2(5-C5H5) and p-G-C6H4SFe(CO)2(5-C5H5) studied using Hartree-Fock and density functional theory methods".http://dx.doi.org/10.1002/poc.3152 (2013).