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| ImageFileL1 = Tributyltin hydride.svg | ImageFileL1 = Tributyltin hydride.svg
| ImageFileL1_Ref = {{chemboximage|correct|??}} | ImageFileL1_Ref = {{chemboximage|correct|??}}
| ImageSizeL1 = 121
| ImageNameL1 = Skeletal formula of tributyltin with one explicit hydrogen added | ImageNameL1 = Skeletal formula of tributyltin with one explicit hydrogen added
| ImageFileR1 = Tributyltin.png | ImageFileR1 = Tributyltin hydride.png
| ImageFileR1_Ref = {{chemboximage|correct|??}} | ImageFileR1_Ref = {{chemboximage|correct|??}}
| ImageSizeR1 = 121
| ImageNameR1 = Spacefill model of tributyltin | ImageNameR1 = Spacefill model of tributyltin
| ImageFile2 = Tributyltin-hydride-3D-balls.png | ImageFile2 = Tributyltin-hydride-3D-balls.png
| ImageFile2_Ref = {{chemboximage|correct|??}} | ImageFile2_Ref = {{chemboximage|correct|??}}
| ImageSize2 = 244
| ImageName2 = Ball and stick model of tributyltin | ImageName2 = Ball and stick model of tributyltin
| SystematicName = Tributylstannane<ref>{{Cite web|url = http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=5948|title = SnBu3H - PubChem Public Chemical Database|work = The PubChem Project|location = USA|publisher = National Center for Biotechnology Information}}</ref> | SystematicName = Tributylstannane<ref>{{Cite web|url = https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=5948|title = SnBu3H - PubChem Public Chemical Database|work = The PubChem Project|location = USA|publisher = National Center for Biotechnology Information}}</ref>
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| CASNo = 688-73-3 | CASNo = 688-73-3
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| UNII_Ref = {{fdacite|correct|FDA}}
| PubChem = 5948
| UNII = 4XDX163P3D
| PubChem_Ref = {{Pubchemcite|correct|pubchem}}
| ChemSpiderID = 5734 | PubChem = 5948
| ChemSpiderID = 5734
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| EINECS = 211-704-4 | EINECS = 211-704-4
| MeSHName = Tributyltin
| ChEBI_Ref = {{ebicite|changed|EBI}} | MeSHName = Tributyltin
| ChEBI_Ref = {{ebicite|changed|EBI}}
| ChEBI = 27086 | ChEBI = 27086
| Beilstein = 3587329 | Beilstein = 3587329
| Gmelin = 4258 | Gmelin = 4258
| SMILES = CCCC(CCCC)CCCC | SMILES = CCCC(CCCC)CCCC
| StdInChI = 1S/3C4H9.Sn.H/c3*1-3-4-2;;/h3*1,3-4H2,2H3;; | StdInChI = 1S/3C4H9.Sn.H/c3*1-3-4-2;;/h3*1,3-4H2,2H3;;
| StdInChI_Ref = {{stdinchicite|changed|chemspider}} | StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = DBGVGMSCBYYSLD-UHFFFAOYSA-N | StdInChIKey = DBGVGMSCBYYSLD-UHFFFAOYSA-N
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} | StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = {{Chem|SnC|12|H|28}} | Formula = {{Chem|SnC|12|H|28}}
| MolarMass = 291.06 g mol<sup>-1</sup> | MolarMass = 291.06 g mol<sup>−1</sup>
| ExactMass = 292.121297467 g mol<sup>-1</sup> | Density = 1.082 g cm<sup>−3</sup>
| BoilingPtC = 80
| Density = 1.082 g cm<sup>-3</sup>
| BoilingPt_notes = at 50&nbsp;Pa
| BoilingPtC = 80
| Solubility = Slowly reacts{{Citation needed|date=September 2012}}
| Boiling_notes = at 50 Pa
| Solubility = Slowly reacts{{Citation needed|date=September 2012}}
}} }}
}} }}
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==Synthesis and characterization== ==Synthesis and characterization==
The compound is produced by reduction of ] with polymethylhydrosiloxane:<ref>{{cite journal|title=Application of Fluoride-Catalyzed Silane Reductions of Tin Halides to the in Situ Preparation of Vinylstannanes|first1=Robert E. |last1=Maleczka|first2=Lamont R. |last2=Terrell|first3=Damon H. |last3=Clark|first4=Susan L.|last4=Whitehead|first5=William P.|last5=Gallagher|first6=Ina |last6=Terstiege|journal=J. Org. Chem.|year=1999|volume=64|issue=16 |pages=5958–5965|doi=10.1021/jo990491+}}</ref><ref>{{cite journal|title=α-D-Ribo-hexofuranose, 3-deoxy-1,2:5,6-bis-''O''-(1-methylethylidene)|first1=J.|last1=Tormo|last2=Fu|first2=G. C.|journal=Org. Synth.|volume=78|page=239|year=2002|doi=10.15227/orgsyn.078.0239}}</ref>
The compound is produced by reduction of ] with polymethylhydrosiloxane (Bu = CH<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>):<ref>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}}</ref><ref>
: 2 "<sub>n</sub>" + (Bu<sub>3</sub>Sn)<sub>2</sub>O "<sub>n</sub>" + 2 Bu<sub>3</sub>SnH
{{OrgSynth
It can also be synthesized by a reduction of ] with ].
|author=Jordi Tormo and Gregory C. Fu
|year=2002
|title=Tributylstannane (Bu<sub>3</sub>SnH)-Catalyzed ] of Alcohols: 3-Deoxy-1,2:5,6-bis-O-(1-methylethyilidine)-α-D-ribo-hexafuranose
|volume=78
|pages=239
|collvol=
|collvolpages=
|prep=}}</ref>


: 2"(MeSiH)" + (Bu<sub>3</sub>Sn)<sub>2</sub>O "(Me<sub>2</sub>Si<sub>2</sub>O" + 2 Bu<sub>3</sub>SnH The hydride is a distillable liquid that is mildly sensitive to air, decomposing to (Bu<sub>3</sub>Sn)<sub>2</sub>O. Its ] exhibits a strong band at 1814&nbsp;cm<sup>−1</sup> for ''ν''<sub>Sn−H</sub>.
:(Bu<sub>3</sub>Sn)<sub>2</sub>O + 2/n (MeSi(H)O)<sub>n</sub> 2 Bu<sub>3</sub>SnH + 1/n <sub>n</sub>
The hydride is a distillable liquid that is mildly sensitive to air, decomposing to (Bu<sub>3</sub>Sn)<sub>2</sub>O. Its IR spectrum exhibits a strong band at 1814 cm<sup>-1</sup> for ν<sub>Sn-H</sub>.


==Applications== ==Applications==
{{See also|Barton–McCombie deoxygenation}}
It is a useful reagent in ]. Combined with ] (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 Bu<sub>3</sub>Sn.<ref name="Clayden">, J. Clayden, N. Greeves, S. Warren and P. Wothers, in ''Organic Chemistry'', 2000, OUP, Oxford, ch. 39, pp. 1040-1041.</ref><ref>T. V. (Babu) RajanBabu, Philip C. Bulman Page, Benjamin R. Buckley, "Tri-n-butylstannane" Encyclopedia of Reagents for Organic Synthesis It is a specialized reagent in ]. Combined with ] (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 Bu<sub>3</sub>Sn<sup>•</sup>.<ref name="Clayden">, J. Clayden, N. Greeves, S. Warren and P. Wothers, in ''Organic Chemistry'', 2000, OUP, Oxford, ch. 39, pp. 1040-1041.</ref><ref>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}}</ref>
2004, John Wiley & Sons. {{doi|10.1002/047084289X.rt181.pub2}}</ref> The radical abstracts a H<sup>•</sup> from another equivalent of tributyltin hydride, propagating the chain. Tributyltin hydride's utility as a H<sup>•</sup> donor can be attributed to its relatively weak bond strength (78 kcal/mol).<ref>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}}</ref>

It is the reagent of choice for ] reactions:<ref>{{cite journal|doi=10.1021/cr9902695|pmid=11749320|title=Metal-Catalyzed Hydrostannations|journal=Chemical Reviews|volume=100|issue=8|pages=3257–3282|year=2000|last1=Smith|first1=Nicholas D.|last2=Mancuso|first2=John|last3=Lautens|first3=Mark}}</ref>
:RC<sub>2</sub>R′ + HSnBu<sub>3</sub> → RC(H)=C(SnBu<sub>3</sub>)R′


==See also== ==See also==
* ] * ]
* ]

== References == == References ==


{{Reflist}} {{Reflist}}
==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}}


] ]
] ]
]
]
]

Latest revision as of 22:34, 23 August 2024

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
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 3587329
ChEBI
ChemSpider
ECHA InfoCard 100.010.642 Edit this at Wikidata
EC Number
  • 211-704-4
Gmelin Reference 4258
MeSH Tributyltin
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/3C4H9.Sn.H/c3*1-3-4-2;;/h3*1,3-4H2,2H3;;Key: DBGVGMSCBYYSLD-UHFFFAOYSA-N
SMILES
  • CCCC(CCCC)CCCC
Properties
Chemical formula SnC
12H
28
Molar mass 291.06 g mol
Density 1.082 g cm
Boiling point 80 °C (176 °F; 353 K) at 50 Pa
Solubility in water Slowly reacts
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

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 "n" + (Bu3Sn)2O → "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 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. 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).

It is the reagent of choice for hydrostannylation reactions:

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
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