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In order to elucidate specific properties of nickel-sulfur complexes, addition and substitution reactions of [Ni(′MeS 2 ′) 2 ] (1) were investigated. 1 is rapidly hydrolyzed by aqueous HCl yielding ′MeS 2 ′–H and Ni(II) ions. 1 coordinates phosphines as coligands, thioether donors decoordinate, however, simultaneously. The monophosphine complex [Ni(PMe3)(′MeS 2 ′ ) 2 ] (2) was characterized by X-ray structure determination. It contains a square-planar NiS 3 P unit and one decoordinated thioether group. Redox reactions of 1 occur with NO +  and NO, yielding the binuclear nitrosyl complexes cis- and trans-[Ni(NO)(′MeS 2 ′)] 2  (3) and the disulfide [′MeS 2 '] 2 •

zeitschrift für naturforschung b

Übergangsmetallkomplexe mit Schwefelliganden, LXXXVI. Säure-Base- und Redox-Reaktionen von [Ni(′MeS 2 ′) 2 ] mit H + , PMe 3 , NO +  und NO. Röntgenstrukturanalyse von [Ni(PMe 3 )(′MeS 2 ′) 2 ] (′MeS2′ = o-(Methylthio)thiophenolat(1–)) / Transition-Metal Complexes with Sulfur Ligands, LXXXVI. Acid-Base and Redox Reactions of [Ni(′MeS 2 ')2] with H + , PMe 3 , NO +  and NO. X-Ray Structure Determination of [Ni(PMe 3 )(′MeS 2 ′)2] (′MeS 2 ′ = o-(methylthio)thiophenolate(1–))