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In order to obtain suitable precursors for iron complexes that model the reactivity of the active sites of nitrogenases, the coordination chemistry of the [Fe(′N 2 H 2 S 2 ′)] fragment was systematically investigated(′N 2 H 2 S 2 ′ 2-  = 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)). One-pot reactions of FeCl 2  -4H 2 O with the tetradentate amine-thiolate ligand ′N 2 H 2 S 2 ′ 2-  and CO, PR 3  or P(OR) 3  yielded the complexes [Fe(CO) 2 (′N 2 H 2 S2′)] (1), [Fe(CO)(PR 3 )(′N 2 H 2 S 2 ′)] (R = Et (2), Pr (3), Bu (4)), [Fe(PMe 3 ) 2  (′N 2 H 2 S 2 ′)] (7), [Fe(dppe)(′N 2 H 2 S 2 ′)] (8 , dppe = 1,2- bis(diphenylphosphine)ethane), and [Fe(P(ÖR) 3 ) 2 (′N 2 H 2 S 2 ′)l (R = Me (9), Pr (10)). Mixed phosphane/phosphite complexes [Fe(PMe 3 )(P(OR) 3 )(′N 2 H 2 S 2 ′)] (R = Me (11), Pr (12)) were synthesized by PMe 3 /P(OPr) 3  exchange of the labile complexes [Fe(PMe 3  ) 2 (′N 2 H 2 S 2 ′)] (7) and [Fe(P(OPr) 3 ) 2 (′N 2 H 2 S2′)] (10). The [Fe(CO)(PR 3 )(′N 2 H 2 S 2 ′)l complexes 3 and 4 also resulted from 1 and PR 3  by photochemical CO substitution. They exhibit characteristic low-frequency v (CO) bands ( ≈1925 cm -1 ), and their remaining CO ligand proved photolytically inert. Reaction of 3 or 4 with NOBF 4  yielded the dinuclear NO complex [Fe(NO)(′N 2 HS 2 ′)] 2  (6 ) which contains two amide functions.

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Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer Fe II -Komplexe mit [FeN 2 S 2 ]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New Fe II  Complexes with [Fe 2 N 2 S 2 ] Cores