Polystannane

Catenation is well established in organotin chemistry and distannane derivatives can be prepared by standard methods (see Ge, p. 396). The compounds are more reactive than organodiger-manes e.g. Sn2Meg (mp 23°) inflames in air at its bp (182°) and absorbs oxygen slowly at room temperature to give (Me2Sn)20. Typical routes to higher polystannanes are ... 

Sita, Lawrence R., Structure/Property Relationships of Polystannanes. 38 189... 

Most of the reactions that can be used to prepare distannanes can be extended to the preparation of oligo- and polystannanes, which have attracted interest for potential use in electronic and optical devices.455 The structures of the products are not necessarily those of completely linear catenanes, (R2Sn) , and different degrees of branching confer different properties. The formation of polymers is also frequently accompanied by the formation of cyclic pentamers or hexamers, and samples prepared by different methods may show substantially different properties. 

The diorganotin dihydrides react with catalysts based on the metallocenes of titanium, zirconium, or hafnium459 162 to give oligo- and polystannanes. 

Much of the interest in the polysilanes, polygermanes, and polystannanes involves their sigma delocalization and their sigma-pi delocalization when coupled with arenes or acetylenes. This is not unexpected since silicon exists as a covalent network similar to diamond. In exhibiting electrical conductivity, germanium and tin show more typical metallic bonding. Some polystannanes have been referred to as molecular metals. ... 

This review will focus on the NMR properties of Zintl ion complexes, namely the solution properties of the ions where E = Si, Ge, Sn, Pb, and the products derived from those clusters. Closely related clusters prepared by other means, such as the recent, elegant organo polystannane work of Schnepf, Power, Huttner, and Fischer, are briefly mentioned but are not the focus of this review. Related overviews of dynamic organometallic complexes [1,2] and the stmcture and bonding of Zintl ions [3-5] can be found in previous reviews and in other chapters of this book. 

Sita LR (1995) Stracture/property Relationships of Polystannanes. In Stone EGA, West R (eds) Advances in organometallic chemistry, vol 38. Academic, London, pp 189-243... 

In recent years, dehydrocoupling reactions catalysed by early transition metal complexes have become an increasingly important method for generating catenated species of the p-block elements. In addition to producing cyclic oligomers, this approach is used to prepare linear oligomers and polymers such as polysilanes and polystannanes of the type H(MR2) H (M = Si, Sn) (see Section 10.1.4). ... 

The condensation of diorganotin dihydrides with diorganotin diamides is another route to cyclic polystannanes. This method is especially useful for the high-yield synthesis of the dimethyl derivative (Me2Sn)g [eqn (10.5)], which cannot be obtained by the dehydrocoupling process. 

Polystannanes would be expected to possess even more o-delocalised structures, as suggested by studies of linear oligostannanes with up to six tin... 

Polystannanes have been shown to display very interesting properties. They are highly photosensitive and exhibit photobleaching behaviour and on UV irradiation depolymerise to yield cyclic oligomers. The materials are thermally stable to 200-270 °C in air and at more elevated temperatures function as precursors to Sn02. " By using rhodium catalysts, branched polystannanes have been prepared. 

The polysilanes can be regarded as one-dimensional analogs to elemental silicon, on which, of course, nearly all of modem electronics is based. The photophysical behavior of polysilanes is not approached by any other materials, save for the less stable and more costly polygermanes and polystannanes. The remarkable properties of polysilanes have led to intense interest, and to numerous proposed high-tech applications. But the great promise of polysilanes as materials has yet to be realized. Their only commercial use at present is as precursors to silicon carbide ceramics, an application which takes no advantage of their optical or electronic properties. 

Highly coordinated tin enolates, reactivity, 9, 362 High-molecular weight polystannanes, preparation and properties, 12, 381... 

D. Redistributive Coupling of Hydrostannanes to Highly Branched Polystannanes. 161... 

As described in Section II.E, polystannanes, which can be prepared by the Wurtz coupling of chlorostannanes with alkali metals and by the dehydrocoupling of hydrostannanes, exhibit intriguing physical properties. The Sita group reported a peculiar polymerization of -Bu2SnH2 with a RhH(CO)(PPh3)3 catalyst [Eqs. (21a) and (21b)].63... 

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