1373719-31-3Relevant academic research and scientific papers
Synthesis, structures, and dearomatization by deprotonation of iron complexes featuring bipyridine-based PNN pincer ligands
Zell, Thomas,Langer, Robert,Iron, Mark A.,Konstantinovski, Leonid,Shimon, Linda J. W.,Diskin-Posner, Yael,Leitus, Gregory,Balaraman, Ekambaram,Ben-David, Yehoshoa,Milstein, David
, p. 9636 - 9649 (2013/09/12)
The synthesis and characterization of new iron pincer complexes bearing bipyridine-based PNN ligands is reported. Three phosphine-substituted pincer ligands, namely, the known tBu-PNN (6-((di-tert-butylphosphino) methyl)-2,2′-bipyridine) and the two new iPr-PNN (6-((di-iso-propylphosphino)methyl)-2,2′-bipyridine) and Ph-PNN (6-((diphenylphosphino)methyl)-2,2′-bipyridine) ligands were synthesized and studied in ligation reactions with iron(II) chloride and bromide. These reactions lead to the formation of two types of complexes: mono-chelated neutral complexes of the type [(R-PNN)Fe(X)2] and bis-chelated dicationic complexes of the type [(R-PNN)2Fe]2+. The complexes [(R-PNN)Fe(X)2] (1: R = tBu, X = Cl, 2: R = tBu, X = Br, 3: R = iPr, X = Cl, and 4: R = iPr, X = Br) are readily prepared from reactions of FeX2 with the free R-PNN ligand in a 1:1 ratio. Magnetic susceptibility measurements show that these complexes have a high-spin ground state (S = 2) at room temperature. Employing a 2-fold or higher excess of iPr-PNN, diamagnetic hexacoordinated dicationic complexes of the type [( iPr-PNN)2Fe](X)2 (5: X = Cl, and 6: X = Br) are formed. The reactions of Ph-PNN with FeX2 in a 1:1 ratio lead to similar complexes of the type [(Ph-PNN)2Fe](FeX4) (7: X = Cl, and 8: X = Br). Single crystal X-ray studies of 1, 2, 4, 6, and 8 do not indicate electron transfer from the FeII centers to the neutral bipyridine unit based on the determined bond lengths. Density functional theory (DFT) calculations were performed to compare the relative energies of the mono-and bis-chelated complexes. The doubly deprotonated complexes [(R-PNN*)2Fe] (9: R = iPr, and 10: R = Ph) were synthesized by reactions of the dicationic complexes 6 and 8 with KO tBu. The dearomatized nature of the central pyridine of the pincer ligand was established by X-ray diffraction analysis of single crystals of 10. Reactivity studies show that 9 and 10 have a slightly different behavior in protonation reactions.
Formation of tertiary amides and dihydrogen by dehydrogenative coupling of primary alcohols with secondary amines catalyzed by ruthenium bipyridine-based pincer complexes
Srimani, Dipankar,Balaraman, Ekambaram,Hu, Peng,Ben-David, Yehoshoa,Milstein, David
supporting information, p. 2525 - 2530 (2013/10/21)
Dehydrogenative coupling of primary alcohols with secondary amines to form tertiary amides and dihydrogen (H2) is efficiently catalyzed by bipyridyl-based ruthenium pincer complexes (0.2-1 mol%) under neutral conditions (in case of the dearomatized complexes), or with added catalytic amount of base. The reaction is sensitive to steric hindrance; in the case of amidation of bulky secondary amines a less sterically hindered complex is more efficient. Selective acylation of primary amines in the presence of secondary amines was also demonstrated. Copyright
