[1.1.1]Propellane is an organic compound, the simplest member of the propellane family. It is a hydrocarbon with formula C5H6 or C2(CH2)3. The molecular structure consists of three rings of three carbon atoms each, sharing one C–C bond.
3D model (JSmol)
|Molar mass||g·mol−1 66.103|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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[1.1.1]Propellane is a highly strained molecule. The bonds of the two central carbon atoms have an inverted tetrahedral geometry, and the length of the central bond is 160 pm. The strength of that bond is disputed; estimates vary from 59–65 kcal/mol to no strength at all. The energy of the biradical state (with no central bond at all) is calculated to be 80 kcal/mol higher. The compound is highly unstable, and at 114 °C it will spontaneously isomerize to 3-methylidenecyclobutene with a half-life of 5 minutes. Its strain energy is estimated to be 102 kcal/mol (427 kJ/mol). Surprisingly, [1.1.1]propellane is persistent at room temperature and is somewhat less susceptible to thermal decomposition than the less strained (90 kcal/mol) [2.2.2]propellane system, which has an estimated half-life of only about 1 h at 25 °C.
Synthesis begins with conversion of the 1,3-di-carboxylic acid of bicyclo[1.1.1]pentane 1 in a Hunsdiecker reaction to the corresponding dibromide 2 followed by a coupling reaction with n-butyllithium. The final product 3 was isolated by column chromatography at −30 °C.
However, a much simplified synthesis was published by Szeimies. It starts with dibromocarbene addition to the alkene bond of 3-chloro-2-(chloromethyl)propene 6 followed by deprotonation by methyllithium and nucleophilic displacements in 7 not isolated but kept in solution at −196 °C.
Acetic acid additionEdit
A radical polymerization initiated by methyl formate and benzoyl peroxide results in a distribution of oligomers. An anionic addition polymerization with n-butyllithium results in a fully polymerized product. X-ray diffraction of the polymer shows that the connecting C–C bonds have bond lengths of only 148 pm.
The compound 1,3-dehydroadamantane, which can be viewed as a bridged [1.3.3]propellane, also polymerizes in a similar way.
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