Zinc‐Contaning Pyridinophanes and Molecular Bowl Assembled Using Zinc and 2,6‐Diamidopyridine Modules

This paper focuses on the targeted synthesis of zinc‐containing pyridinophanes by the condensation reaction of bis(trimethylsilyl)‐ N , N ’‐2,6‐diaminopyridine (bap) with organozinc and zinc halides. By varying the relative stoichiometry of reagents, different molecular entities can be assembled; we have utilized this approach to synthesize a variety of zinc entities. Dinuclear zinc chelate complexes, [{2‐(Me 3 SiN)‐6‐(Me 3 SiNH)C 5 H 3 N}(ZnMe)] 2 ( 1 ), [{2‐(Me 3 SiN)‐6‐(Me 3 SiNH)C 5 H 3 N}(ZnEt)] 2 ( 2 ), first examples of organozinc bridged tetranuclear neutral pyridinophanes [{2,6‐(Me 3 SiN) 2 C 5 H 3 N} 2 (ZnMe) 4 ] ( 3 ) and [{2,6‐(Me 3 SiN) 2 C 5 H 3 N} 2 (ZnEt) 4 ] ( 4 ) have been assembled. Further, mono‐ and dinuclear zinc complexes [2‐(Me 3 SiN)‐6‐(Me 3 SiNH)C 5 H 3 N] 2 Zn[2,6‐(Me 3 SiNH) 2 C 5 H 3 N] ( 5 ), and [{2‐(Me 3 SiN)‐6‐(Me 3 SiNH)C 5 H 3 N} 2 {2,6‐(Me 3 SiN) 2 C 5 H 3 N}]Zn 2 ( 6 ) and trinuclear bowl‐shaped zinc pyridinophane [{2‐(Me 3 SiN)‐6‐(Me 3 SiNH)C 5 H 3 N} 2 {2,6‐(Me 3 SiN) 2 C 5 H 3 N} 2 ]Zn 3 ( 7 ) were also synthesized. A bicyclic pyridinophane, [{2,6‐(Me 3 SiN) 2 C 5 H 3 N} 3 Zn 2 ·2Li] ( 8 ), was obtained by the reaction of zinc halides with lithiated bap. All the new compounds have been spectroscopically characterized using multinuclear NMR and HRMS and structurally characterized by single‐crystal X‐ray diffraction.