02868nas a2200241   4500008004100000245012800041210006900169260000800238300001600246490000700262520200600269100001702275700001902292700001902311700002802330700002502358700002402383700002002407700002502427700002402452700002002476856013002496       2013                        eng d00aSynthesis, structures, and dearomatization by deprotonation of iron complexes featuring bipyridine-based PNN pincer ligands0 aSynthesis structures and dearomatization by deprotonation of iro  cJUL  a9636–96490 v523 a<p>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 KOtBu. 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.</p>1 aZell, Thomas1 aLanger, Robert1 aIron, Mark, A.1 aKonstantinovski, Leonid1 aShimon, Linda, J. W.1 aDiskin-Posner, Yael1 aLeitus, Gregory1 aBalaraman, Ekambaram1 aBen-David, Yehoshoa1 aMilstein, David  uhttps://library.ncl.res.in/content/synthesis-structures-and-dearomatization-deprotonation-iron-complexes-featuring-bipyridine