Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids. Crystal structure and NMR studies of bischelate zinc complex Olexandr I. Guzyr a, * , Leonid N. Markovskii b , Mark I. Povolotskii b , Herbert W. Roesky c , Alexander N. Chernega b , Eduard B. Rusanov b a Institut de Cie `ncia de Materials de Barcelona, Campus U.A.B. 08193 Bellaterra, Spain b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya str.5, 02094 Kiev, Ukraine c Institut fu ¨r Anorganische Chemie der Universita ¨t Go ¨ttingen, Tammannstrabe 4, D-37077 Go ¨ttingen, Germany Received 23 May 2005; received in revised form 17 November 2005; accepted 18 November 2005 Available online 18 January 2006 Abstract Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids are leading to the corresponding bischelate complexes 1–3. Compounds 1–3 were characterized by means of NMR spectroscopy and elemental analysis. The X-ray analysis of [p-MeC 6 H 4 S(O)(Nt-Bu) 2 ] 2 Zn (3) demonstrates a tetrahedral environment of the Zn atom in the solid state and dynamic 1 H NMR studies showed interconvention between two conformers in solution at high temperatures. q 2005 Elsevier B.V. All rights reserved. Keywords: Complexes; Sulfur; Zinc; N ligands; Solid-state structures 1. Introduction The chemistry of main group and transition metal complexes containing sulfur–nitrogen multiple bonded systems as ligands has been widely investigated since the preparation of the first adducts with tetrasulfur tetranitride [1–3]. Such complexes are attracting attention due to their structural peculiarities, such as the coordination fashion of a metal to the ligand, as well as a possible stabilization route for non-isolable under normal conditions intermediates. Among them, compounds containing the NSN fragment as a ligand are of particular interest. Diimides are known to function as mono or bidentante ligands in main group and transition metal complexes [1–5]. Reactions of sulfur diimides with main group metal alkyls, alkoxides or Grignard reagents are leading to a nucleophilic addition to NaS bond, and formation of complexes with the [RNS(R 0 )NR] K ligand [6–9], which subsequently are bonded to transition metals via metathesis reactions [7,10,11]. However, to the best of our knowledge, complexes containing one metal cation and the [RNS(O)(R 0 )NR] K monoanions as bischelating ligands are unknown. One of the synthetic routes for the preparation of main group and transition metal complexes are the reactions, involving the metal alkyls or amides, and compounds containing donor atoms and protic moieties [12]. Among the available reagents main group and transition metals bis(trimethylsilyl) amides are of particular interest due to their high reactivity combined with stability, solubility and easy availability from simple starting materials [13,14]. For instance, it was shown that the reaction of bis[bis(trimethylsilyl)] amides of Zn 2C and Cd 2C with (E–NH) 2 (EZAs, P) four-membered ring systems resulted in the deprotonation of the NH moiety, ring opening, and formation of bischelate complexes with low coordination numbers of As and P (2) respectively [15–17]. Thus, this method was shown to be generally suitable for the synthesis of metal chelate complexes. Due to our broad interest in the chemistry of compounds containing sulfur–nitrogen multiple bonds [18–20], we decided to study the possibility for the preparation of bischelate metal complexes, containing RNS(O)(Ar)NR fragment as a bidentate ligand. As a synthetic route to such type of compounds, we reacted amides of sulfonimidic acids with bis[bis(trimethyl- silyl)] amido zinc. The results of our investigation are presented in the current paper. Journal of Molecular Structure 788 (2006) 89–92 www.elsevier.com/locate/molstruc 0022-2860/$ - see front matter q 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2005.11.021 * Corresponding author. Tel.: C34 93 580 1853x255; fax: C34 93 580 5729. E-mail address: aguzyr@icmab.es (O.I. Guzyr).