Verkade base
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Preferred IUPAC name 2,8,9-Trimethyl-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane | |
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Properties | |
Chemical formula | C9H21N4P |
Molar mass | 216.269 g·mol−1 |
Appearance | colorless oil |
Boiling point | 263.9 °C (507.0 °F; 537.0 K) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references |
In chemistry, the Verkade base (or Verkade superbase) is a powerful superbase with the formula P(MeNCH2CH2)3N. A colorless oil, it is an aminophosphine although its inventor John Verkade called it proazaphosphatrane. The trimethyl derivative or 2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane is the simplest.[1] Diverse analogues of the Verkade base are known, e.g. with isopropyl groups in place of methyl.
Synthesis and reactions
The Verkade base is generated by the reaction of N,N,N-trimethyltren with tris(dimethylamino)phosphine:[2]
- P(NMe2)3 + (MeNHCH2CH2)3N → P(MeNCH2CH2)3N + 3 Me2NH
The principal reaction of the Verkade base is protonation. The proton is attacked by the Verkade base at the phosphorus atom within, which induces the formation of a transannular P-N bond. The product exemplifies the structure of an atrane.
![](http://upload.wikimedia.org/wikipedia/commons/thumb/4/40/VerkadeProtn.svg/290px-VerkadeProtn.svg.png)
The conjugate acid [HP(MeNCH2CH2)3N]+ of the base has a pKa of 32.9 in acetonitrile. For comparison, the conjugate acid of triethylamine has a pKa near 17 in acetonitrile. Owing to its ability to deprotonate weak carbon acids, the Verkade base catalyzes a variety of condensation reactions.
Related compounds
Phosphazenes are phosphorus(V) derivatives with the formula RN=P(NR2)3.
References
- ^ Verkade, John G.; Urgaonkar, Sameer (2012). "Proazaphosphatrane". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn00702.pub2. ISBN 978-0471936237.
- ^ Schmidt, H.; Lensink, C.; Xi, S. K.; Verkade, J. G. (1989). "New Prophosphatranes: Novel intermediates to five-coordinate phosphatranes". Zeitschrift für Anorganische und Allgemeine Chemie. 578: 75–80. doi:10.1002/zaac.19895780109.
- v
- t
- e
- PO3H2−
- P(O–)3
- P2O5·nH2O
- OP(O–)3
- –P(OH)2
- –P(O–)2
- –P(O)(O–)2
- –OP<
- free acid HOP(CF3)2
- HOP(O)<
- PO2H−
2 - –P<
- –P(O)<
- (–O)2PN<
- (–O)2P(O)N<
- e.g. Phosphocreatine
- –OP(N<)2
- –OP(O)(N<)2
- P(N<)3
- e.g. P(NMe2)3
- OP(N<)3
- –NP(N<)3
- –P(O)(O–)N<
- –P(O)(N<)2
- >P(O)N<
- PSxO3−
4-x - (–O)3PS
- (-P)5