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Redox Isomeric Ferrocenyl Styrylruthenium Radical Cations with Diphenyl-Substituted β-Ketoenolato Ligands
Organometallics ( IF 2.8 ) Pub Date : 2019-12-19 , DOI: 10.1021/acs.organomet.9b00714
Christopher Hassenrück 1 , Mykhailo Azarkh 1 , Malte Drescher 1 , Michael Linseis 1 , Serhiy Demeshko 2 , Franc Meyer 2 , Rainer F. Winter 1
Affiliation  

We report on 18-valence-electron ferrocenyl vinylruthenium conjugates 4-Fc-C6H4-CH═CH-Ru(CO)Cl(PiPr3)2(PhR2acac) where PhR2acac denotes a diphenylacetylacetonato ligand with two 4-substituted (R = OMe, 2-OMe; R = H, 2-H; R = F, 2-F; R = CF3, 2-CF3) or perdeuterated (R = C6D5, 2-D) phenyl substituents. The complexes undergo two reversible one-electron oxidations whose potentials depend on the aryl substituents R. The one-electron oxidized forms of these complexes exist as two different isomers, which differ with respect to whether the electron loss has primarily occurred from the ferrocene or the styrylruthenium site. These isomers are clearly distinguished by characteristic features in their infrared, near-infrared, EPR, and Mößbauer spectra. Electron-withdrawing substituents R at the PhR2acac coligand increase the proportion of the ferrocenium-type species, whereas electron-donating ones have the opposite effect.

中文翻译:

带有二苯基取代的β-酮烯醇基配体的氧化还原异构体二茂铁基苯乙烯基钌自由基阳离子

我们报告18价电子二茂铁基乙烯基钌共轭物4-Fc-C 6 H 4 -CH═CH-Ru(CO)Cl(P i Pr 32(Ph R 2 acac)其中Ph R 2 acac表示二苯基乙酰丙酮配位体具有两个4-取代的(R = OME,2-OME ; R = H,2-H ; R = F,2-F ; R = CF 32-CF 3)或全氘化的(R = C 6 d 5二维)苯基取代基。配合物经历两个可逆的单电子氧化,其电势取决于芳基取代基R。这些配合物的单电子氧化形式以两种不同的异构体形式存在,这两种区别在于电子损失主要是由二茂铁引起的还是由二茂铁引起的。苯乙烯钌位点。这些异构体的红外,近红外,EPR和Mößbauer光谱特征鲜明地加以区分。Ph R 2 accocogand上的吸电子取代基R增加了二茂铁型物种的比例,而给电子基具有相反的作用。
更新日期:2019-12-20
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