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Hydrolysis of dinuclear spacer-bridged diorganotin(IV) triflates. A novel cationic double ladder with supramolecular association

journal contribution
posted on 2003-01-01, 00:00 authored by J Beckmann, Dainis Dakternieks, Andrew DuthieAndrew Duthie, Fong Sheen Kuan, E Tiekink
A series of oligomethylene-bridged diorganotin triflates R(OTf)2Sn(CH2)nSn(OTf)2R (R = CH2SiMe3; n = 3, 4, 8, 10) were synthesized by reaction of triflic acid with the precursor oxides R(O)Sn(CH2)nSn(O)R. On the basis of 119Sn NMR (in acetonitrile) the triflates appear to be the simple six-coordinated ionic species [(MeCN)4(RSn(CH2)nSnR)(MeCN)4]2+. These triflates readily undergo hydrolysis to give products, the identity of which depends on the length of the oligomethylene bridge. For n = 3 (5), the solid-state structure shows association of two dimeric units, which results in a tetracationic double ladder. Extensive hydrogen bonding gives rise to a supramolecular association. Solution 119Sn NMR and ES MS suggest some dissociation of 5 into dimers containing four tin atoms and possibly monomers containing two tin atoms. A rudimentary solid-state structure for n = 4 (6) indicates a linear polymer based on dimeric (four tin atoms) units. The structure of 6 also features extensive hydrogen bonding, this time effectively giving rise to alternating layers of cations and anions.

History

Journal

Organometallics

Volume

22

Issue

22

Pagination

4399 - 4404

Publisher

ACS Publications

Location

San Diego, Calif

ISSN

0276-7333

eISSN

1520-6041

Language

eng

Notes

Web Release Date: September 25, 2003

Publication classification

C1 Refereed article in a scholarly journal

Copyright notice

2003, American Chemical Society