Tributyltin hydride

Tributyltin hydride
Skeletal formula of tributyltin with one explicit hydrogen added
Skeletal formula of tributyltin with one explicit hydrogen added
Spacefill model of tributyltin
Spacefill model of tributyltin
Ball and stick model of tributyltin
Names
Systematic IUPAC name
Tributylstannane[1]
Identifiers
3D model (JSmol)
3587329
ChEBI
ChemSpider
ECHA InfoCard 100.010.642 Edit this at Wikidata
EC Number
  • 211-704-4
4258
MeSH Tributyltin
UNII
  • InChI=1S/3C4H9.Sn.H/c3*1-3-4-2;;/h3*1,3-4H2,2H3;; ☒N
    Key: DBGVGMSCBYYSLD-UHFFFAOYSA-N ☒N
  • CCCC[SnH](CCCC)CCCC
Properties
SnC
12H
28
Molar mass 291.06 g mol−1
Density 1.082 g cm−3
Boiling point 80 °C (176 °F; 353 K) at 50 Pa
Slowly reacts[citation needed]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Tributyltin 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:[2][3]

2 "[MeSi(H)O]n" + (Bu3Sn)2O → "[MeSi(OH)O]n" + 2 Bu3SnH

It can also be synthesized by a reduction of tributyltin chloride with lithium aluminium hydride.

The 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 νSn−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•.[4][5] 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).[6]

It is the reagent of choice for hydrostannylation reactions:[7]

RC2R′ + HSnBu3 → RC(H)=C(SnBu3)R′

See also

References

  1. ^ "SnBu3H - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information.
  2. ^ Maleczka, Robert E.; Terrell, Lamont R.; Clark, Damon H.; Whitehead, Susan L.; Gallagher, William P.; Terstiege, Ina (1999). "Application of Fluoride-Catalyzed Silane Reductions of Tin Halides to the in Situ Preparation of Vinylstannanes". J. Org. Chem. 64 (16): 5958–5965. doi:10.1021/jo990491+.
  3. ^ Tormo, J.; Fu, G. C. (2002). "α-D-Ribo-hexofuranose, 3-deoxy-1,2:5,6-bis-O-(1-methylethylidene)". Org. Synth. 78: 239. doi:10.15227/orgsyn.078.0239.
  4. ^ OUP catalogue page, J. Clayden, N. Greeves, S. Warren and P. Wothers, in Organic Chemistry, 2000, OUP, Oxford, ch. 39, pp. 1040-1041.
  5. ^ T. V. (Babu) RajanBabu, Philip C. Bulman Page, Benjamin R. Buckley, "Tri-n-butylstannane" Encyclopedia of Reagents for Organic Synthesis 2004, John Wiley & Sons. doi:10.1002/047084289X.rt181.pub2
  6. ^ 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 doi:10.1021/ar9703443
  7. ^ Smith, Nicholas D.; Mancuso, John; Lautens, Mark (2000). "Metal-Catalyzed Hydrostannations". Chemical Reviews. 100 (8): 3257–3282. doi:10.1021/cr9902695. PMID 11749320.

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. doi:10.1016/S0022-328X(00)81719-2