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The complexes NEt[sub 4] [Fe(NS[sub 3] )(CNR)] (1), [Fe{Fe(NS[sub 3] )(CNR)}[sub 2] -S,S' ] (2), [Co{Fe(NS[sub 3] )(CNMe)}[sub 2] -S,S' ] (3), and [Ni{Fe(NS[sub 3] )(CNMe)}[sub 2] -S,S' ] (4) (R = Me, t-Bu, or C[sub 6] H[sub 11] (Cy)) have been prepared and the X-ray crystal structures of NEt[sub 4] [Fe(NS[sub 3] )(CNMe)] (1a) and [Fe{Fe(NS[sub 3] )(CNCy)}[sub 2] -S,S' ] (2c) have been determined. Mössbauer and IR spectroscopic data and room temperature magnetic moments for these complexes are reported.Key words: iron, cobalt, nickel, thiolate, isocyanide.On a préparé les complexes de NEt[sub 4] [Fe(NS[sub 3] )(CNR)] (1), [Fe{Fe(NS[sub 3] )(CNR)}[sub 2] -S,S' ] (2), [Co{Fe(NS[sub 3] )(CNMe)}[sub 2] -S,S' ] (3) et [Ni{Fe(NS[sub 3] )(CNMe)}[sub 2] -S,S' ] (4) (R = Me, t-Bu ou C[sub 6] H[sub 11] (Cy)) et on a déterminé les structures de NEt[sub 4] [Fe(NS[sub 3] )(CNMe)] (1a) et de [Fe{Fe(NS[sub 3] )(CNCy)}[sub 2] -S,S' ] (2c) par diffraction des rayons X. Pour chacun de ces complexes, on a déterminé les spectres de Mössbauer et IR ainsi que les moments magnétiques à la température ambiante.Mots clés : fer, cobalt, nickel, thiolate, isocyanure.[Traduit par la Rédaction] [ABSTRACT FROM AUTHOR]

Neutral iron complexes of a series of arenephosphinothiol proligands, PhxP(ArSH)3−x, (x=0–2, Ar=C6H4, C6H3SiMe3) have been synthesised. Compounds [Fe{2-(Ph2PO)C6H4S}3] (1), [Fe{2-(Ph2P)-6(Me3Si)C6H3S}3] (2), [Fe{2-(Ph2PO)-6(Me3Si)C6H3S}3] (3) and [Fe2{PhP(C6H4S-2)2}3] (4) were obtained most conveniently by the electrochemical oxidation of an iron anode in a cell containing an acetonitrile solution of the corresponding proligand. [Fe{2-(Ph2P)C6H4S}2(CO)2] (5) was obtained by the addition of the appropriate proligand to an acetonitrile solution of FeCl2 saturated with CO. The reaction of FeCl2 with PhP(C6H4SH-2)2 in methanol in the presence of CO and bis-diphenylphosphinoethane (dppe) gave [Fe{PhP(C6H4S-2)2}(dppe)(CO)] (6) in good yield. The reaction of FeCl2 with the potentially tetradentate P(C6H4SH-2)3 proligand in presence of PMe2Ph or dppe allows the synthesis of [Fe{P(C6H4S-2)3}(PMe2Ph)2] (7) and [Fe{P(C6H4S-2)3}(dppe)] (8). Corresponding reactions of the phosphinothiolates with CoCl2 in the presence of CO and/or phosphine ligands gave [CoCl{PhP(C6H4S-2)2}(dppe)] (9), [Co{PhP(C6H4S-2)2}(dppe)(CO)]BPh4 (10), [Co{PhP(C6H4S-2)2}(dppe) ] (11), [Co(P(C6H4S-2)3L] (L=dppe, 12, L=PMe2Ph, 13. The X-ray crystal structures of complexes 2, 4, 7 and 8, are discussed. [Copyright &y& Elsevier]