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RESEARCH PRODUCT

Ligand substitution in hexahalorhenate(IV) complexes: Synthesis, crystal structures and magnetic properties of NBu4[ReX5(DMF)] (X=Cl and Br)

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Abstract The preparation, crystal structures, and magnetic properties of two rhenium(IV) mononuclear compounds of formula NBu 4 [ReX 5 (DMF)] ( NBu 4 + = tetrabutylammonium cation and DMF = N , N - dimethylformamide ) with X = Cl ( 1 ) and Br ( 2 ) are reported. 1 and 2 are isostructural complexes which crystallize in the monoclinic system with the space group P 2 1 / n . The rhenium atom is six-coordinated with five X atoms and a DMF molecule forming a somewhat distorted octahedral surrounding [values of Re–X varying in the ranges 2.317(1)–2.358(1) ( 1 ) and 2.495(1)–2.518(1) A ( 2 )]. Magnetic susceptibility measurements on samples of 1 and 2 in the temperature range 1.9–300 K are interpreted in terms of magnetically isolated spin quartets with large values of the zero-field-splitting (|2 D | is ca. 20.2 and 39.2 cm −1 for 1 and 2 , respectively).