Efficient Esterification of Ferrocenecarboxylic Acid in Ionic Liquids

An efficient esterification of ferrocenecarboxylic acid with substituted phenols has been achieved using DCC / DMAP protocol in ionic liquids. The corresponding esters are produced in high yields.

Syntheses and Crystal Structures of Bis-[oxo-bis(p-ferrocenylbenzoxy di-n-propyltin)](I) and Bis[oxo-bis(β-ferrocenoylpropionyloxy di-n-propyltin )](II)

Bis-[oxo-bis(p-ferrocenylbenzoxy di-n-propyltin)] I and bis-[oxo-bis(-ferrocenoyl- propionyloxy di-n-propyltin)] II were synthesized and their crystal structures have been determined by X-ray diffraction analysis. The compound I2C6H6 ([(FcC6H4COOSnPr2)2O]22C6H6 or C92H108Fe4O10Sn42C6H6, Mr = 2384.16) is of triclinic, space group P?with a = 12.826(4), b = 13.099(5), c = 17.539(5) ? = 78.229(5), ?= 71.852(5), = 62.746(5)? V = 2483(1) ?, Z = 1, Dc = 1.490 g/cm3, = 0.71073 ? (MoK? =1.611 mm-1 and F(000) = 1128. The structure was refined to R = 0.0491 and wR = 0.1053 for 4690 unique reflections with I > 2(I). The compound IIC6H6 ([(FcCOCH2CH2COOSnPr2)2O]2C6H6 or C80H108Fe4O14Sn4C6H6, Mr = 2115.93) is of triclinic, space group P?with a = 11.260(4), b = 14.126(5), c = 15.961(6) ? = 91.400(6), = 110.654(6), = 104.931(6), V = 2277(1) 3, Z = 1, Dc = 1.510 g/cm3, = 0.71073 ? (MoK? = 1.750 mm-1 and F(000) = 1046. The structure was refined to R = 0.0466 and wR = 0.1138 for 5061 unique reflections with I > 2(I). The two compounds have the similar structures: both are dimers containing centrosymmetric Sn2O2 cores. But there are some differences in the ligating modes between the carboxylate groups and the Sn atoms.

Synthesis, Crystal Structure and Quantum Chemistry Study of Tri(o-bromobenzyl)tin Ferrocenecarboxylate

A novel complex tri（o-bromobenzyl）tin ferrocenecarboxylate has been synthesized and its crystal structure was determined by X-ray diffraction. It belongs to orthorhombic, space group Pbca with a = 1.1340（3）, b = 1.7823 （4）, c = 3.0119（8） nm, V = 6.088（3） nm^3, Mr = 857.81,Z = 8, Dc = 1.872 g/cm^3,μ（MoKα） = 52.63 cm^-1, F（000） = 3328, R = 0.0683 and wR = 0.1057. The tin atom adopts a distorted tetrahedral coordination geometry. Further studies on the title complex have been performed with quantum chemistry calculation at the Lanl2dz basis set level using G98W package. The stability of the complex, some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals have been investigated.

Synthesis and Crystal Structure of N-Phenylbis(ferrocenecarboxyl)imide

The ferrocenyl compound, N-phenylbis（ferrocenecarboxyl）imide （C28H23NO2Fe2, Mr = 517.17）, was synthesized and structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in monoclinic, space group C2/c with a = 21.374（14）, b = 10.430（7）, c = 10.741（7） A, β= 114.184（8）°, V= 2184（2） A^3, Z= 4, Dc = 1.573 g/cm^3, F（000） = 1064, μ（MoKα） = 1.355 mm ^-1, T= 291（2） K, the final R = 0.0548 and wR = 0.1437 for 1524 observed reflections with 1 〉 2σ（I）. In this compound, the nitrogen atom links two ferrocenyl groups and one phenyl group forming a novel imido derivative.

Synthesis of Ferrocene-Modified Carbon Nitride Photocatalysts by Surface Amidation Reaction for Phenol Synthesis

A polymeric Fc-CO-NH-C_(3)N_(4)(Fc-CN)material was synthesized by amidation reaction of ferrocenecarboxylic acid(Fc-COOH)with NH_(2)groups on the surface of mesoporous graphitic carbon nitride(MCN).The properties of the as-synthesized samples were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,UV-Vis diffuse reflectance spectra,N2 adsorption-desorption isotherm,photoluminescence spectroscopy,transmis-sion electron microscopy,electron paramagnetic resonance,(photo)electrochemical measurement and X-ray photo-electron spectroscopy.The resultant catalysts were investigated as heterogeneous catalysts for the selective oxida-tion of benzene to phenol using H_(2)O_(2)as a green oxidant under visible light irradiation.The results reveal that Fc-modified samples can not only extend the visible light absorption,but also accelerate the bulk-to-surface charge transfer and separation via surface dyadic structures,both of which are favorable for phenol production from ben-zene photocatalytic hydroxylation with H_(2)O_(2).Under the optimal conditions,up to 16.9%phenol yield(based on benzene)is obtained by Fc-CN/1.5-5 sample,and the corresponding Fe content is about 0.64 wt%.Furthermore,after the second run,no significant decrease of the activity(in term of TOF)and the selectivity is found in Fc-CN/_(1.0)-5 sample.Combined with the experimental results and Fenton-chemistry,a possible photocatalytic reaction mecha-nism on the hydroxylation of benzene to phenol at neutral medium with visible light is proposed.