Activation of the C-H bond in [(eta(5)-C5H5)Fe(eta(5)-C5H4CH2N(CH3)CH2C6H4R-4)] induced by platinum (II): Crystal structure of sigma-Pt[(eta(5)-C5H5)Fe(eta(5)-C5H3CH2N(CH3)CH2C6H4OCH3-4)]Cl(DMSO)

摘要

Condensations of ferrocenylcarboxaldehyde (1) and p-methyl (2b) or p-chlorobenzylamines (2d) in methanol resulted in ferrocenylaldimines 3b, d which were reduced by lithium aluminum hydride to give 4b, d, respectively. Reductive methylations of 4b, d with aqueous formaldehyde, sodium cyanoborohydride and acetic acid afforded the tertiary ferrocenylamines 5b, d. Treatment of 5a-e [(eta(5)-C5H5)Fe(eta(5)-C5H4CH2N(CH3)CH2C6H4R-4)] (R = CH3O(a), CH3(b), H(c), Cl(d), NO2(e)) with cis-[Pt(DMSO)(2)Cl-2] in methanol produced predominately cycloplatinated complexes 6a-e sigma-Pt[(eta(5)-C5H5)Fe(eta(5)-C5H3CH2N(CH3)CH2C6H4-R-4)]Cl(DMSO) (R = same as before) in which the configurations consisted of RNRP and SNSP, In addition, the preferred activation of the C-H bond in the cyclopentadienyl ring rather than that in the phenyl ring was also observed. All compounds 3b-5b, 3d-5d, 6a-e were characterized by elemental analysis, IR and H-1 NMR. The structure of 6a was determined by X-ray single crystal diffraction. The possible mechanism for the formation of 6 was discussed. (C) 2006 Elsevier Ltd. All rights reserved.