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{{chembox |
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{{chembox |
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|Watchedfields = changed |
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| verifiedrevid = 398513311 |
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|verifiedrevid = 430575274 |
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| ImageFile = PMDTA.png |
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|ImageFile = PMDTA.png |
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| ImageSize = 200px |
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|ImageFile_Ref = {{chemboximage|correct|??}} |
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| IUPACName = N,N,N',N',N''-Pentamethyldiethylenetriamine |
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|ImageSize = 160 |
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| OtherNames = Pentamethyldiethylenetriamine,<br /> PMDTA, <br /> PMDETA, <br /> PMDT, <br /> pmdien, <br /> Me<sub>5</sub>dien, <br /> 1,2-Ethanediamine, <br /> N-(2-(dimethylamino)ethyl)-N,N',N'-trimethyl- |
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|ImageName = Skeletal formula of PMDTA |
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(9CI), <br /> 1,1,4,7,7-Pentamethyldiethylenetriamine, <br /> 2,5,8-Trimethyl-2,5,8-triazanonane |
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|ImageFile1 = PMDTA-3D-balls.png |
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| Section1 = {{Chembox Identifiers |
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|ImageFile1_Ref = {{chemboximage|correct|??}} |
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| CASNo_Ref = {{cascite}} |
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|ImageName1 = Ball and stick model of PMDTA |
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| CASNo = 3030-47-5 |
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|ImageFile2 = PMDTA-3D-spacefill.png |
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| PubChem = 18196 |
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|ImageFile2_Ref = {{chemboximage|correct|??}} |
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}} |
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|ImageName2 = Spacefill model of PMDTA |
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| Section2 = {{Chembox Properties |
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|PIN = ''N''<sup>1</sup>--''N''<sup>1</sup>,''N''<sup>2</sup>,''N''<sup>2</sup>-trimethylethane-1,2-diamine |
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| C=9|H=23|N=3 |
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|Section1={{Chembox Identifiers |
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| Appearance = liquid |
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|CASNo = 3030-47-5 |
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| Density = 0.83 g/cm<sup>3</sup> |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| Solubility = sl sol H<sub>2</sub>O; <br /> sol ethanol, acetone, ethers, alkanes |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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| MeltingPt = -20 °C |
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|UNII = 3274UTY3HL |
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| BoilingPt = 198 °C |
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|PubChem = 18196 |
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}} |
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|ChemSpiderID = 17187 |
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| Section7 = {{Chembox Hazards |
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|ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| MSDS = |
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|EINECS = 221-201-1 |
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| RPhrases = {{R22}} {{R24}} {{R34}} |
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|UNNumber = 2734 |
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| SPhrases = {{S26}} {{S36/37/39}} {{S45}} |
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|ChEBI = 39475 |
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}} |
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|ChEBI_Ref = {{ebicite|changed|EBI}} |
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|RTECS = IE2100000 |
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|Beilstein = 1741396 |
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|Gmelin = 27747 |
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|SMILES = CN(C)CCN(C)CCN(C)C |
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|StdInChI = 1S/C9H23N3/c1-10(2)6-8-12(5)9-7-11(3)4/h6-9H2,1-5H3 |
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|StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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|StdInChIKey = UKODFQOELJFMII-UHFFFAOYSA-N |
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|StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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|Section2={{Chembox Properties |
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|C=9 | H=23 | N=3 |
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|Appearance = Colorless liquid |
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|Odor = Fishy, ammoniacal |
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|Density = 830 mg mL<sup>−1</sup> |
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|MeltingPtC = -20 |
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|BoilingPtC = 198 |
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|VaporPressure = 31 Pa (at 20 °C) |
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|RefractIndex = 1.442 |
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|Section3={{Chembox Hazards |
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|ExternalSDS = |
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|GHSPictograms = {{gHS corrosion}} {{gHS skull and crossbones}} |
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|GHSSignalWord = '''DANGER''' |
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|HPhrases = {{h-phrases|302|311|314}} |
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|PPhrases = {{p-phrases|280|305+351+338|310}} |
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|FlashPtC = 53 |
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|AutoignitionPtC = 155 |
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|ExploLimits = 1.1–5.6% |
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|LD50 = {{unbulleted list|232 mg kg<sup>−1</sup> <small>(dermal, rabbit)</small>|1.351 g kg<sup>−1</sup> <small>(oral, rat)</small>}} |
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|Section4={{Chembox Related |
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|OtherFunction_label = amines |
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|OtherFunction = {{unbulleted list| ]|]|]|]}} |
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'''PMDTA''', formally N,N,N',N',N"-pentamethyldiethylenetriamine, is an organic compound with the formula <sub>2</sub>NMe (Me is CH<sub>3</sub>). PMDTA is a basic, bulky, and flexible, tridentate ligand that is a used in ]. |
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'''PMDTA''' ('''''N'',''N'',''{{prime|N}}'',''N{{prime}}{{prime}}'',''N{{prime}}{{prime}}''-pentamethyldiethylenetriamine''') is an organic compound with the formula <sub>2</sub>NCH<sub>3</sub>. PMDTA is a basic, bulky, and flexible, ] that is a used in ]. It is a colorless liquid, although impure samples appear yellowish. |
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==Synthesis== |
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==Synthesis== |
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PMDTA is prepared by methylating ] with formaldehyde and ].<ref>{{cite journal | journal = ] | year = 1951 | pages = 924–931 | doi = 10.1002/hlca.19510340327 | title = Über die stufenweise Quaternisierung von aliphatischen Polyaminen. Neue Verbindungen mit ganglienblockierender Wirkung | author = A. Marxer, K. Miescher | volume = 34 | issue = 3}}</ref> |
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PMDTA is prepared from ] by the ], involving the use of formaldehyde and ].<ref>{{cite journal |author1=Marxer, A. |author2=Miescher, K. | title = Über die stufenweise Quaternisierung von aliphatischen Polyaminen. Neue Verbindungen mit ganglienblockierender Wirkung | journal = ] | year = 1951 | volume = 34 | issue = 3 | pages = 924–931 | doi = 10.1002/hlca.19510340327 }}</ref> |
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: + 5 CH<sub>2</sub>O + 5 HCO<sub>2</sub>H → 5 CO<sub>2</sub> + 5 H<sub>2</sub>O |
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:(H<sub>2</sub>N<sub>2</sub>)<sub>2</sub>NH + 5 CH<sub>2</sub>O + 5 HCO<sub>2</sub>H → (Me<sub>2</sub>N<sub>2</sub>)<sub>2</sub>NMe + 5 CO<sub>2</sub> + 5 H<sub>2</sub>O |
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==Comparison with diethylenetriamine== |
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==Dien versus PMDTA== |
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Unlike diethylenetriamine, all three amines in PDMTA are tertiary. Both PMDTA and dien are tridentate ligands that form two five-membered chelate rings. The σ-donating properties of the amino groups of dien are greater than that of PMDTA in copper(II) complexes.<ref name = Angelici>{{cite journal | author = Angelici, R. J.; Allison, J. W. | year = 171 | title = Stability Constants for Amino Acid Coordination bySubstituted Diethylenetriamine Complexes of Copper(I1) and the Kinetics of Amino Acid Ester Hydrolysis | journal = ] | volume = 10 | pages = 2238–2243 | doi = 10.1021/ic50104a30}}</ref> Both ligands can coordinate metal complexes in arrangements where the three nitrogen centers are co-planar or mutually cis. |
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Unlike diethylenetriamine, all three amines in PMDTA are tertiary. Both PMDTA and diethylenetriamine are tridentate ligands that form two five-membered chelate rings. The σ-donating properties of the amino groups of diethylenetriamine are greater than that of PMDTA in copper(II) complexes.<ref name = Angelici>{{cite journal |author1=Angelici, R. J. |author2=Allison, J. W. | title = Stability Constants for Amino Acid Coordination by Substituted Diethylenetriamine Complexes of Copper(II) and the Kinetics of Amino Acid Ester Hydrolysis | journal = ] | year = 1971 | volume = 10 | issue = 10 | pages = 2238–2243 | doi = 10.1021/ic50104a030}}</ref> Both ligands can coordinate metal complexes in arrangements where the three nitrogen centers are co-planar or mutually ''cis''. |
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==Organolithium compounds and PMDTA== |
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==Organolithium compounds and PMDTA== |
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Alkyllithium compounds such as ] (BuLi) are used to deprotonate weak acids, e.g. hydrocarbons. It is well known that organolithium aggregates are broken up by Lewis bases to give reagents that EW a more efficient base than untreated BuLi.<ref name = strohmann>{{cite journal | author = Strohmann, C. and Gessner, V. H. | year = 2007 | title = From the Alkyllitium Aggregate ditertiary amine ] is used in these applications; it binds to the lithium center as a bidentate ligand. PMDTA behaves analogously, but since it is tridentate, it binds more strongly to lithium. In contrast to TMEDA, PMDTA forms monomeric complexes with organolithium compounds. Both amines affect the regiochemistry of metalation.<ref name=strohmann/><ref>{{cite journal |
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PMDTA is used to modify the reactivity of ]s, which deaggregate in the presence of Lewis bases to enhance their reactivity.<ref name = strohmann>{{cite journal |author1=Strohmann, C. |author2=Gessner, V. H. | title = From the Alkyllitium Aggregate (nBuLi)<sub>2</sub>·PMDTA<sub>2</sub> to Lithiated PMDTA | journal = ] | year = 2007 | volume = 46 | issue = 24 | pages = 4566–4569 | doi = 10.1002/anie.200605105 }}</ref> Commonly, the ''di''tertiary amine ] is used in these applications; it binds to the lithium center as a bidentate ligand. PMDTA behaves analogously, but since it is tridentate, it binds more strongly to lithium. In contrast to TMEDA, PMDTA forms monomeric complexes with organolithium compounds. Both amines affect the regiochemistry of metalation.<ref name=strohmann/><ref>{{cite encyclopedia | author = Fraenkel, G. | title = PMDTA | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | pages = 806–813 | year = 2002 | publisher = Wiley-VCH | location = Weinheim | doi = 10.1002/047084289X.rp028 | isbn = 0-471-93623-5}}</ref> |
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| author = Fraenkel, G. |
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| title = PMDTA |
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| journal = Encyclopedia of Reagents for Organic Synthesis |
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| pages = 806–813 |
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| year = 2002 |
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| publisher = Wiley-VCH |
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| location = Weinheim |
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| doi = 10.1002/047084289X.rp028}}</ref> |
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In the PMDTA-n-BuLi adducts, the Li-C bonds are highly polarized, thus increasing the basicity of the butyl group.<ref name = elschenbroich>{{cite journal | author = Elschenbroich, C. | year = 2006 | title = Wiley-VCH: Weinheim | journal = ] | volume = 5.1 | pages = 45–46 | isbn = 978-3-29390-6}}</ref> |
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In the PMDTA/''n''-BuLi adducts, the Li-C bonds are highly polarized, thus increasing the basicity of the butyl group.<ref name = elschenbroich>{{cite book | author = Elschenbroich, C. | year = 2006 | publisher = Wiley-VCH | location = Weinheim | title = Organometallics | pages = 45–46 | isbn = 978-3-527-29390-2}}</ref> |
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The effect of PMDTA on lithium anilide is illustrative of PMDTA's complexing power. The complex, , is trinuclear, featuring approximately colinear Li<sup>+</sup> centers that are three-, four-, and five-coordinate. The central three-coordinate lithium atom is not bonded to PMDTA. One of the terminal Li centers is pseudo-tetrahedral in an N<sub>4</sub> coordination sphere. The other terminal lithium atom is five-coordinate and binds to two anilino N centers and the PMDTA.<ref>{{cite journal | author = Barr, D.; Clegg, W.; Cowton, L.; Horsburgh, L.; Mackenzie, F. M.; Mulvey, R. | year = 1995 | title = Lithium Anilide Complexed by pmdeta: Expectations of a simple monomer, but in Reality an Odd Trinuclear Composition Combining Three-, Four-, and Five-coordinate Lithium | journal = ] | volume = 8 | pages = 891–892 | doi = 10.1039/C39950000891 | issue = 8}}</ref> |
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The effect of PMDTA on lithium anilide is illustrative of PMDTA's complexing power. The complex, , is trinuclear, featuring approximately colinear Li<sup>+</sup> centers that are three-, four-, and five-coordinate. The central three-coordinate lithium atom is not bonded to PMDTA. One of the terminal Li centers is pseudo-tetrahedral in an N<sub>4</sub> coordination sphere. The other terminal lithium atom is five-coordinate and binds to two anilino N centers and the PMDTA.<ref>{{cite journal |author1=Barr, D. |author2=Clegg, W. |author3=Cowton, L. |author4=Horsburgh, L. |author5=Mackenzie, F. M. |author6=Mulvey, R. | title = Lithium Anilide Complexed by pmdeta: Expectations of a simple monomer, but in Reality an Odd Trinuclear Composition Combining Three-, Four-, and Five-coordinate Lithium | journal = ] | year = 1995 | volume = 1995 | issue = 8 | pages = 891–892 | doi = 10.1039/C39950000891}}</ref> |
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==Transition metal and aluminium complexes== |
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==Transition metal and aluminium complexes== |
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PMDTA often forms five-coordinate complexes due to steric bulk of the methyl groups. PMDTA stabilize unusual cations. The first cationic derivative of alane. <sup>+</sup><sup>-</sup> was prepared by treating H<sub>3</sub>AlNMe<sub>3</sub> with PMDTA.<ref name = elschenbroich/> |
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PMDTA often forms five-coordinate complexes due to steric bulk of the methyl groups. PMDTA stabilize unusual cations. The first cationic derivative of alane, <sup>+</sup><sup>−</sup> was prepared by treating H<sub>3</sub>AlNMe<sub>3</sub> with PMDTA.<ref name = elschenbroich/> |
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==References== |
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==References== |
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