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Synthesis and spectroscopic identification of a mu-1,2-disulfidodinickel complex.

ABSTRACT: Reduction of elemental sulfur by a monovalent nickel precursor leads to a trans-1,2-mu-disulfidodinickel(II) complex assigned based on a combination of advanced spectroscopic methods in conjunction with density functional theory calculations. The disulfido linkage is characterized by an intense optical S --> Ni charge transfer transition at 650 nm, which causes a significant distortion of the Ni(2)S(2) core along an isotope-sensitive v(S-S) mode at 474 cm(-1), as demonstrated by the resonance Raman excitation profile of this vibrational feature.

SUBMITTER: Kieber-Emmons MT

PROVIDER: S-EPMC3370929 | biostudies-literature | 2009 Jan

REPOSITORIES: biostudies-literature

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Synthesis and spectroscopic identification of a mu-1,2-disulfidodinickel complex.

Kieber-Emmons Matthew T MT Van Heuvelen Katherine M KM Brunold Thomas C TC Riordan Charles G CG

Journal of the American Chemical Society 20090101 2

Reduction of elemental sulfur by a monovalent nickel precursor leads to a trans-1,2-mu-disulfidodinickel(II) complex assigned based on a combination of advanced spectroscopic methods in conjunction with density functional theory calculations. The disulfido linkage is characterized by an intense optical S --> Ni charge transfer transition at 650 nm, which causes a significant distortion of the Ni(2)S(2) core along an isotope-sensitive v(S-S) mode at 474 cm(-1), as demonstrated by the resonance Ra ...[more]

PMID: 19099477

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| S-EPMC2960972 | biostudies-literature

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Project description:Bis(carboranyl)amides 1,1'-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1'-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1'-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7'(8')-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2-. The attempted reaction of [7,7'(8')-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2- with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3'-Gd(1,2-C2B9H11)2]- as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

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