Synthesis and structure Of [(C5H5)Fe(C5H5)Fe(C5H4PS2OCH2C6H4N3)(-), a new phosphonodithioate derivative, and its coordination chemistry with rhodium(I) and nickel(II)

The anion [(C5H5)Fe(C5H4PS2OCH2C6H4N3)](-) (1) was synthesized in two steps from ferrocene, P4S10 and hydroxymethylbenzotriazole in the presence of tr iethylamine. The molecular structure of 1, determined by single-crystal X-r ay structure analysis of the triethylammonium salt, shows the rare R(R 'O)P S2 arrangement in the expected tetrahedral geometry; the substituents R = f errocenyl and R ' = methylenbenzotriazol impose a certain rigidity on the m olecule. Anion 1 reacts with [RhCl(cod)](2) (cod = 1,5-cyclooctadiene) to g ive Rh(cod)[(C,H,)Fe(C5H4PS2OCH2C6H4N3)] (2) and with [RhCl(CO)(2)](2) to g ive Rh(CO)(2)[(C5H5)Fe(C5H4PS2OCH2C6H4N3)] (3). With [NiCl2(C4Me4)](2) anio n I gives the analogous nickel complex Ni(C4Me4)[(C5H5)Fe(C5H4PS2OCH2C6H4N3 )] (4). However, with NiCl2. 6H(2)O the anion 1 loses the methylenebenzotri azol unit to give the complex Ni[(C5H5)Fe(C5H4PS2O)](2) (5). The expected c omplex Ni[(C5H5)Fe(C5H4PS2OCH2C6H4N3)](2) (6) was obtained from the room-te mperature reaction of I with anhydrous NiCl2 in aqueous acetonitrile. The s ingle-crystal X-ray structure analyses reveal a tetrahedral rhodium coordin ation geometry for 2 and a square-planar nickel coordination geometry for 5 . (C) 2001 Elsevier Science B.V. All rights reserved.