On the Reaction of Elemental Tin with Alcohols: A Straightforward Approach to Tin(II) and Tin(IV) Alkoxides and Related Tinoxo Clusters

Abstract

Extending the classical reactivity pattern of tin: Elemental tin reacts with alcohols to give, depending on the identity of the alcohol and the reaction conditions, a variety of tin alcoholates and tinoxo clusters (see scheme).

Hydrolysis of bis(dimethylamido)tin to tin (II) oxyhydroxide and its selective transformation into tin (II) or tin (IV) oxide

“…In this context it is desirable to develop solution-processable precursors that convert to the desired product at low temperature [16]. Molecular precursors, e.g., [Sn(µ-ONep) 2 ] ∞ (ONep = OCH 2 CMe 3 ) or its hydrolysis products [Sn 5 (µ 3 -O) 2 (µ-ONep) 6 ] [Sn 6 (µ-O) 4 (ONep) 4 ] [17], Sn 6 O 4 (O t Bu) 4 [18], Sn 6 O 4 (OSiMe 3 ) 4 [19] and mixed alkoxide-ketoester complexes of Ti, Zr and Hf of the type M(OR)(R´) (where R = Me, Et, i Pr, t Bu, R´= acetylacetonato) have been shown to possess these properties. The decomposition and reactivity of these precursors can be tuned by the ligand sphere around the metal atom to produce functional materials SnO x (x = 1 -2) [17,19], TiO 2 , ZrO 2 and HfO 2 [20].…”

Perfluorinated tert‐Butoxides of Tin(II): The Dimeric Alkoxide and Its Monomeric Ate Complex

“…The easiest conceivable synthetic route to Sn(O R F ) 2 , would be the reaction of tin metal with an excess of the pure alcohol, as reported for Sn(O n Bu) 2 . In contrast, upon addition of tin metal to pure anhydrous HO R F almost no hydrogen gas was evolving.…”

“…Hence, only very little reaction took place. Note that problems for this synthetic route were already described for HO t Bu instead of HO n Bu …”

“…Tin(II) alkoxides are known already since the first preparations of Sn(OMe) 2 and Sn(OEt) 2 in 1963 respectively 1967. First NMR experiments of these alkoxides together with Sn(O n Bu) 2 were published a few years later , . Numerous other tin(II) alkoxides were structurally characterized yielding monomeric, dimeric,, , , or polymeric, , structures and depending on the bulk of the alkoxy group or additional interactions as in Sn(OCH 2 CH 2 NMe 2 ) 2 (Figure ).…”

The amino alcohol MeN(CH2CMe2OH)2

“…Some representatives of these compounds have also characterized by single-crystal X-ray diffraction analysis (Churakov et al, 2009). In the context with our long-standing interest in tin and silicon derivatives of amino alcohols (Berends et al, 2009;Glowacki et al, 2016Glowacki et al, , 2017Gock et al, 2013;Iovkova-Berends, Berends, Zö ller, Schollmeyer et al, 2012;Lutter et al, 2012;Zö ller et al, 2011Zö ller et al, , 2012Zö ller & Jurkschat, 2013), we report here the crystal structure of the title compound (Fig. 1).…”