Synthesis and Characterization of a Series of Structurally and Electronically Diverse Fe(II) Complexes Featuring a Family of Triphenylamido-Amine Ligands

Abstract

A family of triphenylamido-amine ligands of the general stoichiometry L x H 3 = [R-NH-(2-C 6 H 4 )] 3 N (R = 4-t-BuPh (L 1 H 3 ), 3,5-t-Bu 2 Ph (L 2 H 3 ), 3,5-(CF 3 ) 2 Ph (L 3 H 3 ), CO-t-Bu (L 4 H 3 ) 3,5-Cl 2 Ph (L 5 H 3 ), COPh (L 6 H 3 ), CO-i-Pr (L 7 H 3 ), COCF 3 (L 8 H 3 ), i-Pr (L 9 H 3 )) has been synthesized and characterized, featuring a rigid triphenylamido-amine scaffold and an array of stereoelectronically diverse aryl, acyl and alkyl substituents (R). These ligands are deprotonated by potassium hydride in THF or DMA and reacted with anhydrous FeCl 2 to afford a series of ferrous complexes, exhibiting stoichiometric variation and structural complexity. The prevalent (Figures S1-S6). Summary of X-ray crystallographic data for the same compounds (Table S1). X-ray crystallographic data for all structurally characterized compounds in CIF format. Mössbauer spectra of compounds 5, 6, 8, 9, 13, 14 ( Figures S7-S12). Cyclic voltammograms of compounds 5-15 ( Figures S13-S26). The material is available free of charge via the Internet at http://pubs.acs.org. NIH Public Access

Catalytic polymerization of olefins and cycloolefins with transition metal complexes

“…Contributions from ligand-centered events cannot be excluded at the present time, especially for Co-3, for which a large i p,a value was observed. These results are consistent with the electronic character of the ligands and prior electrochemical data obtained for the analogous Fe II complexes, 69 although the potentials of the Co II compounds have been shifted anodically, as expected, by a factor of 0.4-0.7 V.…”

“…The structures of the Mn II These results were consistent with the electronic character of the ligands and prior electrochemical data obtained for the analogous Fe II complexes, 69 although the potentials of the Mn II compounds were shifted anodically, as expected, by a factor of 0.4-0.6 V.…”

“…Figures [66][67][68][69][70] show the relevant experiments and Table 25 summarizes the results of that study. W 2 -PDCPD gels showed the highest absorption capability for CHCl 3 (14 g of solvent/g of gel), followed by 1,3-dichlorobenzene W 2 -PDCPD gels exhibited remarkably higher uptakes (~ 12× higher for CHCl 3 , and ~ 4× higher for CH 2 Cl 2 ) than those reported for disulfide-linked polymeric state NMR data and it was found that the ratio of NBE/NBD units was relative to the monomer molar ratio in the reaction mixture.…”

Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents

“…The family of trisphenylamido-amine ligands (L 1 H 3 –L 17 H 3 ) employed in this study is shown in Figure . The majority of these ligands (L 1 H 3 –L 15 H 3 ) have been used and reported in previous studies. − They are all derivatives of the common 2,2′,2″-triaminotriphenylamine framework, featuring carbonaceous arm substituents (alkyl, aryl acyl). Ligand L 16 H 3 is prepared by methylation of deprotonated (KH) 2,2′,2″-triaminotriphenylamine by MeI in THF, and ligand L 17 H 3 is derived via condensation of the same triamine with the corresponding chiral acyl chloride in the presence of Et 3 N in dichloromethane.…”

Synthesis, Antioxidant Activity and Fluorescence Properties of Novel Europium Complexes with (E)-2- or 4-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide Schiff Base

“…[7][8][9][10][11] Organic rare earth complexes have garnered growing interest due to their potential application as fluorescent probes, labels in biological immunoassay applications, as optical amplifiers 12,13 and as active central species in photoluminescent materials. 14,15 Due to the unique photophysical and photochemical properties of rare earths complexes which exhibit potential to be harnessed in the development of new photodynamic therapies, they offer exciting opportunities to elucidate the structural features of nucleotides such as DNA.…”