Organotin Oxygen Compounds

Organotin compounds are important industrial chemicals. One major use is as stabilizers for poly(vinyl chloride) (PVC) plastics. These additives, one example of which is dioctyltinmaleate, inhibit degradation of the polymer by heat, light, and oxygen. In the absence of these tin compounds, PVC yellows and becomes brittle. 

One of the first reported couplings of GC-ICP-MS was by Van Loon et al. [115], who used a coupled system for the speciation of organotin compounds. A Perkin-Elmer Sciex Elan quadrupole mass filter instrument was used as the detector with 1250 or 1500 W forward power. The GC system comprised a Chromasorb column with 8 ml min 1 Ar/2 ml min-1 02 carrier gas flow with an oven temperature of 250°C. The interface comprised a stainless-steel transfer line (0.8 m long) which connected from the GC column to the base of the ICP torch. The transfer line was heated to 250°C. Oxygen gas was injected at the midpoint of the transfer line to prevent carbon deposits in the ICP torch and on the sampler cone. Carbon deposits were found to contain tin and thus proved detrimental to analytical recoveries. Detection limits were in the range 6-16 ng Sn compared to 0.1 ng obtained by ETAAS, but the authors identified areas for future improvements in detection limits and scope of the coupled system. 

Stille coupling was also developed in tlie early 1980s and is similar to Suzuki coupling in its sequence. It is used to couple aryl or vinyl halides or triflates with organotin compounds via oxidative addition, transmetallation, and reductive elimination. The oxidative addition reaction has tlie same requirements and preferences as discussed earlier for tlie Heck and Suzuki reactions. The reductive elimination results in formation of tlie new carbon-carbon bond. The main difference is that tlie transmetallation reaction uses an organotin compound and occurs readily without the need for an oxygen base. Aryl, alkenyl, and alkyl stannanes are readily available. Usually only one of tlie groups on tin enters into... 

Organotin compounds are widely used as stabilisers for PVC. They are usually stabilised with R2SnX2 compounds, where R is the alkyl, and X is oxygen, ester, mercaptide, acetyl and other groups. 

Figure 2.17. Electron spectroscopy for chemical analysis ESCA) spectra of organometallic polymer films before and after exposure to oxygen plasma. The silicon 2p transition page 99) is shifted from 99.7 to 102.4 eV. The magnitude of the shift is consistent uMh conversion to SiO, where x is between 1.5 and 2. The Sn 3d transitions of the organotin compound above) undergo a similar shift 1.7 eV), consistent with generation of a SnOx surface, where x is again between 1.5 and 2. Argon sputter etching followed by ESCA analysis indicates that these oxide films are less than 100 A thick.

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