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RESEARCH PRODUCT

The First Examples of a Crown Ether Intramolecularly Encapsulating Mono- and Diorganotin Dications: Synthesis and Structures of [PhSnCH2([16]crown-5)][ClO4]2and [HOSnCH2([16]crown-5)][Y]2(Y=ClO4, CF3SO3)

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description

The reaction of silver perchlorate with [PhI 2 SnCH 2 ([16]crown-5)] (1) and [I 3 SnCH 2 ([16]crown-5)] (2) gave the organotin(IV)-substituted crown ether complexes [PhSnCH 2 ([16]crown-5)][ClO 4 ] 2 (3) and [HOSnCH 2 ([16]crown-5)][Y] 2 (4: Y= ClO 4 , 5: Y=CF3 S 03 ) , respectively. All compounds have been isolated as air-stable materials and characterised by 1 H, 13 C, 119 Sn and 119 Sn MAS (5) NMR spectroscopy, ESIMS spectrometry, elemental analysis and by single-crystal X-ray diffraction analysis. The molecular structures of 3-5 show that the tin(IV) cation fits perfectly into the crown ether cavity and is coordinated by the five oxygen atoms of the ring to give a pentagonal bipyramidal configuration about the central metal cation. Notably, compounds 4 and 5 contain the first monomeric monoorganotin dication. Moreover, there are 3 J( 1 H, 119 Sn) coupling constants to the CH 2 CH proton of 377 (3) and 470 Hz (4, 5) that are, to the best of our knowledge, the biggest such couplings ever reported.