Syntheses and Structures of Bisamidinate-Alane Complexes

Bayram, Melike GND; Bläser, Dieter; Wölper, Christoph GND; Schulz, Stephan GND

Insertion reactions of α,ω-bis-carbodiimides (RNCN)2X (15: R = Et, t-Bu, Ph; X = C3H6, C4H8) with 2 equiv of AlMe3 yielded the dinuclear tethered bis-amidinate–alane complexes [RNC(Me)NAlMe2]2X (R = Et, X = C4H8 (6); R = t-Bu, X = C3H6 (7), C4H8 (8)). Analogous reactions with 4 equiv of AlMe3 resulted in the coordination of two additional AlMe3 molecules, yielding the tetranuclear bis-amidinate complexes [EtN(AlMe3)C(Me)NAlMe2]2X (X = C3H6 (9), C4H8 (10)) and [t-BuNC(Me)N(AlMe3)AlMe2]2X (X = C3H6 (11), C4H8 (12)). In addition, equimolar reactions between (RNCN)2X (R = Et, X = C3H6, C4H8; R = Ph, X = C4H8) and 2 equiv of AlMe3 at elevated temperatures occurred with intramolecular cyclization and formation of [EtNC(Me)NC3H6N(AlMe3)CNEt]AlMe2 (13) and [RNC(Me)NC4H8N(AlMe3)CNR]AlMe2 (R = Et (14), Ph (15)). Hydrolysis of 11 gave the protonated free ligand PhNC(Me)NC4H8N(H)CNPh (16) in high yield. 616 were characterized by elemental analyses, multinuclear NMR (1H, 13C) and IR spectroscopy, and single-crystal X-ray diffraction (7, 1014, 16).


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Bayram, M., Bläser, D., Wölper, C., Schulz, S., 2020. Syntheses and Structures of Bisamidinate-Alane Complexes.
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