Kristallstrukturen von TMEDA‐Addukten und Salzen mit protonierten TMEDA‐Molekülen

Crystal Structures of TMEDA Adducts and of Salts with Protonated TMEDA Molecules The reaction of TMEDA with two equivalents of BH₃(SMe₂)] in toluene at 20 °C gives the adduct TMEDA(BH₃)₂] ( 1 ). A similar reaction of pyrrolidine with BH₃(SMe₂)] in a molar ratio of 1:1 leads to the adduct pyrrolidine(BH₃)] ( 2 ). TMEDA can be introduced into the coordination sphere of In³⁺ by the treatment of InI₃ with TMEDA in toluene to give the complex InI(TMEDA)] ( 3 ). The salt HTMEDA]I ( 4 ), containing a mono‐protonated TMEDA molecule, is the result of the reprotonation of NH₄]I and TMEDA in toluene at 20 °C. The salts H₂TMEDA]—InCl₄(TMEDA)]₂ ( 5 ) and H₂TMEDA]InCl₅(THF)] ( 6 ) are formed in the reaction mixtures TMEDA/toluene/InCl₃/HCl and TMEDA/toluene/THF/InCl₃/HCl, respectively, whereupon 6 was characterized more closely. Crystals of In₅I₆(OH)(TMEDA)₄]I·2, 5toluene ( 7 ·2.5toluene) can be obtained after treatment of InI₃ with non‐dried TMEDA; 4 was identifed as by‐product. 1 — 7 ·2.5toluene were partially investigated by NMR methods and vibrational spectroscopy. In all cases a characterization by single crystal X‐ray diffraction was performed. According to this, all nitrogen atoms in 1 and 2 are coordinated by BH₃ groups leading to a distorted tetrahedral environment at the nitrogen and the boron atoms. In 3 a distorted trigonal‐bipyramidal coordination sphere at the In³⁺ is present. The apical positions are occupied by I3 and N3. Strong N‐H···N bridges, running along 001] is the feature in 4 ; the ^I—‐Ions are not involved into the system of H‐bridges. A ion triple, H₂TMEDA]InCl₄(TMEDA)]₂, hold together by bifurcated H‐bridges is the dominating structural motif in 5 , whereas alternation bifurcated and linear H‐bridges, leading zu a zig‐zag chain along 100], is the build‐up principle of 6 . In 7 ·2.5toluene a complex In₅O₈ skeleton was formed, consisting of a virtual corner‐connected doubled heterocubane. At every heterocubane a corner, occupied by a metal ion, is missing. The coordination spheres of the In atoms of the complex cation are completed by TMEDA molecules and iodide ions.