Low temperature synthesis, magnetic and electrical properties of iron–magnesium superparamagnetic nanoalloy

1H NMR assignment corrections and 1H, 13C, 15N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline

“…It is really surprising, however, that their assignments were inconsistent, although the spectral patterns of such highly symmetric [M(LL) 3 ] 2+ cations were relatively simple, containing two doublets [H(3)/H(6)] and two triplets [H(4)/H(5)] for LL = bpy, or two doublets [H(2)/H(4)], a doublet of doublets [H(3)] and a singlet [H(5)] for LL = phen. Particularly, the predominantly suggested orders of the 1 H resonances, H(3) > H(4) > H(5)/H(6) for [M(bpy) 3 ] 2+ 2, 3, 8–13, 15–17, 19–22 and H(4) > H(5) > H(2) > H(3) for [M(phen) 3 ] 2+ ,7, 9, 24, 26–28, 30, 31 contrasted to those proposed by some other authors: H(6) > H(3) > H(4) > H(5),1 H(6) > H(4) > H(3) > H(5),4 H(6) > H(5) > H(3) > H(4),5–7 H(3) > H(6) > H(5) > H(4)14 (all for [M(bpy) 3 ] 2+ ) and H(4) > H(2) > H(5) > H(3),29 H(2) > H(4) > H(3) > H(5),14 H(2) > H(3) > H(4) > H(5),19 H(2) > H(5) > H(4) > H(3),23, 32 H(2) > H(4) > H(5) > H(3)25 (all for [M(phen) 3 ] 2+ ). In our opinion, very large variations cannot be caused by the change of solvent and/or counterions, but they reflect erroneous attributions in some articles (the largest differences concerned peaks with the same multiplicity: H(3)/H(6) and H(4)/H(5) in bpy; H(2)/H(4) in phen).…”

“…The 1 H NMR data for their salts were assigned in case of [Fe(bpy) 3 ]Cl 2 ,1 [Fe(bpy) 3 ](ClO 4 ) 2 ,2 [Fe(bpy) 3 ](PF 6 ) 2 ,3 [Ru(bpy) 3 ] Cl 2 ,4–7 [Ru(bpy) 3 ](SCN) 2 ,8 [Ru(bpy) 3 ](ClO 4 ) 2 ,2, 9 [Ru(bpy) 3 ] (PF 6 ) 2 ,10–18 [Ru(bpy) 3 ](BF 4 ) 2 ,19, 20 [Os(bpy) 3 ]Cl 2 ,5 [Os(bpy) 3 ] (ClO 4 ) 2 ,2, 21 [Os(bpy) 3 ](PF 6 ) 2 22 and [Fe(phen) 3 ](ClO 4 ) 2 ,23, 24 [Ru(phen) 3 ]Cl 2 ,7, 25–27 [Ru(phen) 3 ](ClO 4 ) 2 ,9, 14, 24, 28 [Ru(phen) 3 ] (PF 6 ) 2 ,29 [Ru(phen) 3 ](BF 4 ) 2 ,19 [Ru(phen) 3 ]SO 4 ,30 [Os(phen) 3 ] Cl 2 ,31 [Os(phen) 3 ](CF 3 SO 3 ) 2 32. It is really surprising, however, that their assignments were inconsistent, although the spectral patterns of such highly symmetric [M(LL) 3 ] 2+ cations were relatively simple, containing two doublets [H(3)/H(6)] and two triplets [H(4)/H(5)] for LL = bpy, or two doublets [H(2)/H(4)], a doublet of doublets [H(3)] and a singlet [H(5)] for LL = phen.…”

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX2 (Ch=Se, Te; X=Cl, Br)

“…The primary difference from the DAB congeners is that the released bipy ligand forms an insoluble complex with the MgCl 2 byproduct, thereby eliminating the need for column chromatography. [31] Most interesting is that compound 6 serves as a functional equivalent of TeCl 2 . This is a significant discovery as the free binary halide is unknown in the condensed phase, and thus the reactivity of the tellurium dihalides is completely unexplored.…”

“…The [Se(bipy)Cl 2 ] complex 5 also reacts with the Grignard reagents to form aryl selenides. The primary difference from the DAB congeners is that the released bipy ligand forms an insoluble complex with the MgCl 2 byproduct, thereby eliminating the need for column chromatography 31. Most interesting is that compound 6 serves as a functional equivalent of TeCl 2 .…”

“…[9] There exist several different methods for making SeX 2 and all suffer from the drawback that the resultant selenium dihalide must be used in situ, and cannot be stored for later use. [9][10][11] Complicating matters, there is no simple method of readily ascertaining exactly what is present in solution-that is, how pure the SeCl 2 is after, for example, 4 or 5 h. Selenium-77 NMR spectroscopy is relatively simple using modern spectrometers, but obtaining a reasonable 77 Se NMR spectrum in a short timeframe is not as facile as it is for other routine nuclei (e.g., 1 H, 13 C, 31 P, 19 F). Moreover, a 5-10 % impurity is not easily observed in a routine sample analyzed by 77 Se NMR spectroscopy, even though it may be a significant detriment to any attempted transformations.…”