Hydrolysis of Dinuclear Spacer-Bridged Diorganotin(IV) Triflates. A Novel Cationic Double Ladder with Supramolecular Association

Abstract

A series of oligomethylene-bridged diorganotin triflates R(OTf)2Sn(CH2) n Sn(OTf)2R (R = CH2SiMe3; n = 3, 4, 8, 10) were synthesized by reaction of triflic acid with the precursor oxides R(O)Sn(CH2) n Sn(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) n SnR)(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.

Sulfonate-bonded tin complexes for the production of diphenyl carbonate

“…The distance between Sn and the triflato oxygen for the hydrated A in comparison with that in the non-hydrated complex 1a, implying a significant electron donation from H 2 O to the electrophilic Sn atom. The anhydrous and hydrated tin complexes are likely to form a polymeric structure through interaction of triflate oxygen of hydrated complex 1b to the tin atom of anhydrous complex 1a [14,15]. The interaction between two molecules can be clearly seen in the packing diagram shown in Fig.…”

Hypercoordinated organotin triflates

“…24 The presence of intramolecularly coordinated ligands in diorganotin triflates may prevent the condensation and formation of species having hydroxy and/or oxo groups. This was recently demonstrated for a series of bis(lactamo-…”

A novel two-dimensional organostannoxane coordination network promoted by phenazine: Synthesis, characterization and X-ray structure of

“…Metal coordinated trifluoromethanesulfonate ligands are known to adopt a large diversity of bonding modes, ranging from the ionic, to mono-, bi-or tridentate, terminal or bridging [41]. Numerous examples of trifluoromethanesulfonate derivatives have been reported previously in organotin(IV) chemistry [42,43], displaying in particular excellent Lewis-acid catalytic properties for organic reactions, such as Mukaiyama aldol reaction [44], Robinson annulation [45], acetylation of alcohols [46], and transesterification of dimethyl carbonate with phenol [47]. Lately, we isolated and described the crystallographic structure of the two-dimensional hydroxo di-n-butylstannane derivative catena-…”