Tributyltin hydride explained

Jaikatyltin hydride is an organotin compound with the formula (C₄H₉)₃SnH. It is a colorless liquid that is soluble in organic solvents. The compound is used as a source of hydrogen atoms in organic synthesis.

Synthesis and characterization

The compound is produced by reduction of tributyltin oxide with polymethylhydrosiloxane:^{[1] [2]}

2 "[MeSi(H)O]_n" + (Bu₃Sn)₂O → "[MeSi(OH)O]_n" + 2 Bu₃SnHThe hydride is a distillable liquid that is mildly sensitive to air, decomposing to (Bu₃Sn)₂O. Its IR spectrum exhibits a strong band at 1814 cm⁻¹ for ν_Sn−H.

Applications

See also: Barton–McCombie deoxygenation. It is a specialized reagent in organic synthesis. Combined with azobisisobutyronitrile (AIBN) or by irradiation with light, tributyltin hydride converts organic halides (and related groups) to the corresponding hydrocarbon. This process occurs via a radical chain mechanism involving the radical Bu₃Sn^•.^{[3] [4]} The radical abstracts a H^• from another equivalent of tributyltin hydride, propagating the chain. Tributyltin hydride's utility as a H^• donor can be attributed to its relatively weak bond strength (78 kcal/mol).^[5]

It is the reagent of choice for hydrostannylation reactions:^[6]

RC₂R′ + HSnBu₃ → RC(H)=C(SnBu₃)R′

See also

• Tributyltin
• Trimethylsilyl

Further reading

• Hayashi, K.; Iyoda, J.; Shiihara, I. "Reaction of organotin oxides, alkoxides and acyloxides with organosilicon hydrides. New preparative method of organotin hydrides " J. Organomet. Chem. 1967, 10, 81.

Notes and References

1. Application of Fluoride-Catalyzed Silane Reductions of Tin Halides to the in Situ Preparation of Vinylstannanes. Robert E. . Maleczka. Lamont R. . Terrell. Damon H. . Clark. Susan L.. Whitehead. William P.. Gallagher. Ina . Terstiege. J. Org. Chem.. 1999. 64. 16 . 5958–5965. 10.1021/jo990491+.
2. α-D-Ribo-hexofuranose, 3-deoxy-1,2:5,6-bis-O-(1-methylethylidene). J.. Tormo. Fu. G. C.. Org. Synth.. 78. 239. 2002. 10.15227/orgsyn.078.0239.
3. http://www.oup.com/uk/catalogue/?ci=9780198503460 OUP catalogue page
4. T. V. (Babu) RajanBabu, Philip C. Bulman Page, Benjamin R. Buckley, "Tri-n-butylstannane" Encyclopedia of Reagents for Organic Synthesis2004, John Wiley & Sons.
5. Laarhoven, L. J. J.; Mulder, P.; Wayner, D.D. M. "Determination of Bond Dissociation Enthalpies in Solution by Photoacoustic Calorimetry" Acc. Chem. Res. 1999, 32, 342
6. 10.1021/cr9902695. 11749320. Metal-Catalyzed Hydrostannations. Chemical Reviews. 100. 8. 3257–3282. 2000. Smith. Nicholas D.. Mancuso. John. Lautens. Mark.