Triorganotin Derivatives

Synth By rxn. of (Me3Sn)20 with NaNH2 in Et20, in 70-80% yield ( 71)  

Bis(trimethyltin) Methylamide (M-475) Sn2(VH2iN Synth. By rxn. of Me3SnCl with MeNHLi in Et20-petr. 

By rxn. of He SnCl with PhNHLl In Et20-petr. 

By transamination of Me3SriNEt2 with PhNH2, in 90 yield (251), and derivatives, in 78% yield (27O5). 

By rxn. of MeoSnCl with Me2NLi in EtgO-petr. ether, in 91% yield 

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Triorganotin derivatives of 1 -phenyl- 17/-tetrazole-5-thiol also tend to self-assemble in the solid state359-361. For example, tribenzyltin 1 -phenyl-1H-tetrazole-5-thiolate, Bz3SnSCN4Ph (161), forms a linear coordination polymer with intermolecular Sn—N distances of 2.559(12) and 2.676(10) A and intramolecular Sn—S distances of 2.565(4) A359, whereas trimethyltin 1-phenyl-177-tetrazole-5-thiolate, Me3SnSCN4Ph360, self-assembles to give trimers. 

Various monohalides of triorganotin derivatives have been shown by NMR spectroscopy to ionize in polar solvents, providing the corresponding coordinated cations . Solutions of tributyltin or triphenyltin chloride, perchlorate and tetrafluoroborate have been studied by Edlund and coworkers in dichloromethane, sulfolane, acetonitrile, pyridine, DMPU, DMSO and HMPA (Table 6). They reported the most downfield Sn NMR chemical shift of 220 ppm for n-Bu3Sn+ C104 in dichloromethane and showed that the Sn NMR... 

Figure 2.5.2 Most common coordination environments for tin macrocycles, cages and coordination polymers (a) monoorganotin (b) diorganotin (c) triorganotin derivatives. R = organic group, X = ligand with functional groups containing C, N, O, S, etc.

An alternative approach involves the polymerization of a suitable tin-containing monomer, 4 and was recently employed by Angiolini and coworkers,33 with the preparation of grafted organotin carboxylates by copolymerization of triorganotin derivatives of p-vinylbenzoic acid (p-VBA) with styrene and 1,4-divinylbenzene. 

N-Substituted triorganotin derivatives of acetamide, MeC(=0)NMeSnMc3 and MeC(=0)N(SnMe3)2, are also associated by Sn --0 secondary bonds to form chain-like arrays 88 and 89 [245]. 

Fascinating supramolecular structures have been identified in the solid state of triorganotin tetrazoles [294-296]. Nitrogen-tin interactions between adjacent molecules lead to supramolecular self-assembly of triorganotin derivatives into helical chains, 123, and of functionalized polytetrazoles, e.g. 124, into two-dimensional layers and three-dimensional networks with large channels. 

O-TRIORGANOTIN DERIVATIVES OF OXIMES AND HYDROXYLAMINES All compounds are listed in Table I78. 

Triorganotin derivatives of unsaturated monocar-boxylic acids are listed in Table 199 Triorganotin half esters of unsaturated dicarboxylic acids are summarized in Table 200 Tables 205 and 206 include bis(triorganotin)carboxylates of unsaturated dicarboxylic acids and of polyfunctional acids, respectively. Additional references to triorganotin car-boxylates of unsaturated acids may be found in Chapter 8.1. 

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