Reactions With Esters, Halides, and Halogenoids. I. Bis-(Triethyltin) Oxide and Sulfide

Abstract

In Group IV-regular there is a gradual increase in basicity from the nearly neutral carbon to the clearly basic tin; this order of increasing basicity depends on experimental results mainly in aqueous or non-aqueous solutions.An exploratory publication on organogermanium esters established (Et3Ge)20 as the most basic, (Et2GeO)4 as the next most basic and [(EtGeO)20]n as the least basic ethylgermanium oxide (1). This work suggested that bis-(trialkyltin) oxides would react with numerous acids weaker than acetic acid; recent researches at this Institute demonstrate the reaction of (Et3Sn)20 with H2S or C2H6SH (2), or with HCN (3). This present paper, exploratory in nature, clearly demonstrates the capture of halogen, halogenoid, or an ester group by tin at the expense of silicon, germanium, phosphorus, arsenic, or antimony. It also shows the transfer of halogen from tin of a higher oxidation number to tin of a lower oxidation number.

On the reactivity of metal and organometallic halides toward R3SnOSnR3 systems

“…Both tin-oxygen and tin-carbon bonds in bis(triorganotin) oxide were found to be prone to attack by TeCl 4 and PhTeCl 3 . Cleavage of tincarbon bond from R n SnR 4−n compounds employing TeCl 4 and PhTeCl 3 is well established and has been used as a convenient method for the preparation of organotellurium compounds in high yield and high purity [8,9].…”

“…In sharp contrast to well-documented reactions of metallic and organometallic halides with tetraorganotins and hexaorganoditins, those involving R 3 Sn O SnR 3 compounds have been studied to a limited extent [1,2]. Action of silicon, tin, and phosphorus-halides on organotin oxides has been reported to produce organotin halides [3] whereas reaction of vinylmagnesium chloride with (Bu 3 Sn) 2 O yielded tributylvinyltin [4].…”

“…Action of silicon, tin, and phosphorus-halides on organotin oxides has been reported to produce organotin halides [3] whereas reaction of vinylmagnesium chloride with (Bu 3 Sn) 2 O yielded tributylvinyltin [4]. Reactions of organometallic halides with diorganotin oxides have also been studied [3].…”

“…Action of silicon, tin, and phosphorus-halides on organotin oxides has been reported to produce organotin halides [3] whereas reaction of vinylmagnesium chloride with (Bu 3 Sn) 2 O yielded tributylvinyltin [4]. Reactions of organometallic halides with diorganotin oxides have also been studied [3]. Datta et al [5] reported the action of mercuric halides on bis(triphenyltin) oxides in an attempt to isolate R 3 Sn O HgCl compounds parallel to earlier reported reactions of AlX 3 (X = Cl, Br) with R 3 Si O SiR 3 , which produced stable and isolable R 3 SiOAlX 2 compounds [6].…”

“…Reactions of organometallic halides with diorganotin oxides have also been studied [3]. Datta et al [5] reported the action of mercuric halides on bis(triphenyltin) oxides in an attempt to isolate R 3 Sn O HgCl compounds parallel to earlier reported reactions of AlX 3 (X = Cl, Br) with R 3 Si O SiR 3 , which produced stable and isolable R 3 SiOAlX 2 compounds [6]. Interaction of (R 3 Sn) 2 O with thionylchloride, SOCl 2 to give organotinhalides has also been investigated [7].…”