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The reactions of [Fe('pyS 4 ')] 2  with PMe 3  , PnPr 3  , N 2 H 4  and pyridine afforded mononuclear [Fe(L)('pyS 4 ')] complexes with L = PMe 3  ( 1 ), PnPr 3  (2 ), N 2 H 4  (3) and pyridine (4). NMR spectroscopy, magnetic measurements and X-ray structure determinations revealed that all complexes exhibit frans-thiolate donors and low-spin Fe II  centres, irrespective of the σ-π or σ ligand character of L. In this regard, the properties of [Fe(L)('pyS 4 ')] complexes strongly contrast with those of [Fe(L)('NHS 4 ')] complexes ('N H S 4 ' 2-  = 2 ,2 '-bis(2 -mercaptophenylthio)- diethylamine(2 -)) and indicate that the rigid py(CH 2 ) 2  entity of the 'pyS 4  2-  ligand is able to enforce trans configurations and low-spin states of complexes with [FeNS 4  ] cores. In spite of their diamagnetism, confirming the absence of antibonding electrons, all complexes 1 to 4 are highly reactive and rapidly exchange their L ligands for CO to give [Fe(CO)('pyS 4 ')]. Evidence was obtained that the oxidation of [Fe(N'-H 4 )('pyS 4 ')] (3) yields the diazene complex [μ-N 2  H 2  {Fe('pyS 4 ’)} 2 ] (5).

zeitschrift für naturforschung b

Transition Metal Complexes with Sulphur Ligands, Part 151 [1]. Ligand Enforced Configurations and Low-Spin States of [FeNS 4 ] Cores in [Fe II (L)('pyS 4 ')] Complexes with σ and σ-π Ligands (L = N 2 H 4 , pyridine, PMe 3 , PnPr 3 ; 'pyS 4 ' 2-  = 2,6-bis(2-mercaptophenylthiomethyl)pyridine (2-))