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Chemical synthesis and structural analysis reveals selective sodium cation binding by substituted benzomolybdacrown ethers, indicating size-dependent alkali metal encapsulation.
The reaction of the diphosphanes 2a‐i with (OC)4Mo(nbd) under high dilution conditions affords the mononuclear benzomolybdacrown ethers cis‐(OC)4Mo{1,2‐, 1,3‐, 1,4‐[PH2PCH2(CH2OCH2)πCH2]2C6H4‐P, P′] (3a‐i) (n = 1, 2). On the basis of the 31P nucleus the inclusion behavior of the molydacycles 3a‐i toward the alkali metal salts LiBF4 and NaBPh4 was investigated with the aid of a NMR titration technique by using the program EQNMR. Only 3dshows an interaction with the alkali metal cation Na+ forming a 1:1 and 2:1 complex (3d/cation) while no interaction with Li+ could be detected. The molecular structures of 3a and 3d were elucidated by X‐ray structural analyses. Complexes 3a and 3d crystallize in the monoclinic space groups P21/c and P21/n with Z = 8 and 4, respectively.
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Lindner et al. (1997) studied this question.
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