Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi - 221 005, UP, India.
Dalton Trans. 2012 Jul 28;41(28):8556-66. doi: 10.1039/c2dt30212h. Epub 2012 May 31.
The synthesis and characterization of multinuclear complexes [Pd(acac)(fcdpm)] (1), [Pd(fcdpm)(2)] (2), [Co(acac)(fcdpm)(2)] (3), [Co(fcdpm)(3)] (4) and α-alkoxy derivatives [α-OMe-fcdpm] (5), [α-OEt-fcdpm] (6), [α-OPr(n)-fcdpm] (7) and [α-OBu(n)-fcdpm] (8) (fcdpm = 5-ferrocenyldipyrromethene; acac = acetylacetone) have been described. Formation of alkoxy derivatives 5-8 takes place from highly selective Fe(III) mediated alkoxylation of fcdpm in alcohol. It has been established that yield of α-alkoxy derivatives depend on the alcohol chain length. The compounds under study have been characterized by elemental analyses, spectral (IR, (1)H, (13)C NMR, ESI-MS, UV-vis) and electrochemical studies (CV and DPV). Structures of 1, 3 and 5 have been verified by X-ray single crystal analyses. Structural studies revealed distorted square planar and octahedral geometry about Pd(II) and Co(III) centres. All the compounds exhibited oxidation wave due to Fc/Fc(+) redox couple (0.34-0.36, 1-4; 0.24-0.25 V, 5-8).
已合成并表征了多核配合物[Pd(acac)(fcdpm)]（1）、[Pd(fcdpm)(2)]（2）、[Co(acac)(fcdpm)(2)]（3）、[Co(fcdpm)(3)]（4）和α-烷氧基衍生物[α-OMe-fcdpm]（5）、[α-OEt-fcdpm]（6）、[α-OPr(n)-fcdpm]（7）和[α-OBu(n)-fcdpm]（8）（fcdpm=5-二茂铁基二吡咯甲川；acac=乙酰丙酮）。烷氧基衍生物 5-8 的形成是通过 fcdpm 在醇中高度选择性的 Fe(III)介导烷氧基化反应得到的。已经确定α-烷氧基衍生物的产率取决于醇链的长度。所研究的化合物通过元素分析、光谱（IR、（1）H、（13）C NMR、ESI-MS、UV-vis）和电化学研究（CV 和 DPV）进行了表征。通过 X 射线单晶分析验证了 1、3 和 5 的结构。结构研究表明，Pd(II)和 Co(III)中心具有扭曲的平面四方和八面体几何构型。所有化合物都表现出由于 Fc/Fc(+)氧化还原对（0.34-0.36，1-4；0.24-0.25 V，5-8）引起的氧化波。
