Addition of elemental sulfur to the vanadium nitride [(nacnac)V≡N(OAr)] forms the first thionitrosyl complex of vanadium, [(nacnac)V(NS)(OAr)]. Single crystal X-Ray diffraction studies and DFT calculations reveal an almost linear thionitrosyl ligand resulting from an extended π-resonance across the VNS moiety.
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Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.
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The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [Tc(NS)Cl(PPh)] () and [Tc(NS)Cl(PPh)(OPPh)] () and their reaction products with hydrotris(pyrazolyl)borates, {HB(pz)}. Similar reactions were conducted with [Tc(NO)Cl(PPh)(CHCN)] and related rhenium thionitrosyls. Remarkably, most such reactions result in a rapid cleavage of the boron-nitrogen bonds of the ligands and the formation of pyrazole complexes of the two group 7 metals.
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Dalton Trans
January 2020
Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
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Dalton Trans
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Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China.
Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)].
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Chem Commun (Camb)
April 2013
Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN, USA.
Addition of elemental sulfur to the vanadium nitride [(nacnac)V≡N(OAr)] forms the first thionitrosyl complex of vanadium, [(nacnac)V(NS)(OAr)]. Single crystal X-Ray diffraction studies and DFT calculations reveal an almost linear thionitrosyl ligand resulting from an extended π-resonance across the VNS moiety.
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Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark.
The novel S = 1/2 thionitrosyl complexes Cr(NS)(CN)(5)(3-), Cr(NS)(dmso)(5)(2+), and Cr(NS)(nmf)(5)(2+) (dmso = dimethyl sulfoxide, nmf = N-methylformamide) have been prepared, and their optical and electron paramagnetic resonance (EPR) spectra were studied. The values of the isotropic and anisotropic hyperfine and superhyperfine coupling constants A((53)Cr), A((14)N), and A((13)C) and of g were determined from the EPR spectra at room temperature and at 66 K. The values of A(⊥) and A(iso) in the thionitrosyl complexes were slightly higher than in the analogous nitrosyl complexes.
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