0000000001319046
AUTHOR
Karolin Kobalz
Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni II 2 (L)(μ 1,1 -N 3 )][ClO 4 ] (L = Macrocyclic N 6 S 2 Ligand)
International audience; The dinuclear Ni-II complex [Ni-2(L-2)][ClO4](2) (3) supported by the 28-membered hexaaza-dithiophenolate macro-cycle (L-2)(2-) binds the N-3(-) ion specifically end-on yielding [Ni-2(L-2)(mu(1,1)-N-3)] [ClO4] (7) or [Ni-2(L-2)(mu(1,1)-N-3)][BPh4] (8), while the previously reported complex [Ni2L1(mu(1,3)-N-3)][ClO4] (2) of the 24-membered macrocycle (L-1)(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH center dot center dot center dot pi interactions …
CCDC 1437970: Experimental Crystal Structure Determination
Related Article: Alexander Jeremies, Sina Gruschinski, Michel Meyer, Vitaly Matulis, Oleg A. Ivashkevich, Karolin Kobalz, and Berthold Kersting|2016|Inorg.Chem.|55|1843|doi:10.1021/acs.inorgchem.5b02743