Showing papers by "Stanislav Groysman published in 2015"
TL;DR: In this paper, aryl azides with methyl or ethyl groups in the ortho positions of the phenyl ring react catalytically via nitrene coupling to give azoarenes.
39 citations
TL;DR: In this paper, the synthesis of Cr imido complexes in bis(alkoxide) ligand environments and their nitrene transfer reactivity with isocyanides was reported, where the reaction of Cr2(OR)4 (OR = OCtBu2Ph) with bulky aryl or alkyl azide results in the formation of the trigonal-planar Cr(IV) mono(imido) complexes Cr(or)2(NR1)1, whereas less bulky anisomethane azides form the Cr(VI) bis(
38 citations
TL;DR: NMR studies indicated that the reduction of Cu(II) to Cu(I) is accompanied by the oxidation of the alkoxide RO(-) to form the alkoxy radical RO(•), which subsequently forms tert-butyl phenyl ketone by β-scission.
Abstract: Treatment of NiCl2(dme) and NiBr2(dme) (dme = dimethoxyethane) with 2 equiv of LiOR (OR = OCtBu2Ph) forms the distorted trigonal planar complexes [NiLiX(OR)2(THF)2] (THF = tetrahydrofuran) 5 (X = Cl) and 6 (X = Br). The reaction of CuX2 (X = Cl, Br) with 2 equiv of LiOR affords the Cu(I) product Cu4(OR)4 (7). The same product can be obtained using the Cu(I) starting material CuCl. NMR studies indicated that the reduction of Cu(II) to Cu(I) is accompanied by the oxidation of the alkoxide RO– to form the alkoxy radical RO•, which subsequently forms tert-butyl phenyl ketone by β-scission. Treatment of compounds 1–4 ([M2Li2Cl2(OR)4], M = Cr–Co) with thallium hexafluorophosphate allowed the isolation of the distorted tetrahedral complexes of the form M(OR)2(THF)2 for M = Mn (8), Fe (9), and Co (10). Cyclic voltammetry performed on compounds 8–10 demonstrated irreversible oxidations for all complexes, with the iron complex 9 being the most reducing. Complex 9 shows a reactivity toward PhIO and Ph3SbS to form th...
28 citations
TL;DR: Unlike the previously reported square-planar bis(ketimino)pyridine nickel chloride, the present species demonstrate N(py)-Ni-X angles of 156°-162° and significant spin density at the metal inferred from EPR measurements and DFT calculations.
16 citations