Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 1 / 0067 110

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We will also forego discussion of any substituted polyene wherein the substituent is not hydrocarbyl (i.e. composed of any elements other than hydrogen and carbon). This decision does not arise out of lack of interest in these species per se, but rather, that discussion of many of the relevant compounds has been presented in earlier thermochemistry chapters elsewhere in other volumes in the ‘Functional Groups’ series. For example, the energetics of the X D O containing divinyl ether, 8; furan, 9; and 1,6-oxido[10]annulene (also known as 11-oxa-bicyclo[4.4.1]deca-1,3,5,7,9-pentaene), 10; have been recently discussed in the Supplement E2 volume of this series1 and therein were explicitly compared with those of their corresponding hydrocarbon analogs with X D CH2, 1,4-pentadiene, cyclopentadiene and 1,6-methano[10]annulene, respectively. The O vs CH2 comparison was shown to be generally interesting and informative where it can be made. The available thermochemical data are disappointingly sparse. For example, there are no thermochemical data for either pyran isomer, 11 or 12 with X D O, to include with discussions of the corresponding X D CH2 species, the isomeric 1,3- and 1,4-cyclohexadienes that are discussed at some length in Section V.D of the current chapter. Indeed, not even all hydrocarbyl substituents and their ancillary functionalities and features will be discussed in the current chapter. We now acknowledge we will largely omit discussion of homoaromatic species such as cyclopropanated species and their comparison with the formally related compounds having CDC bonds. Inclusion of this interrelation is quite superfluous in the current chapter since it figured prominently in a recent review of the thermochemistry of cyclopropanes2.

B. What Do We Mean By Thermochemistry?

As has been the approach for most of the author’s other reviews on organic thermochemistry, the current chapter will be primarily devoted to the relatively restricted scope of ‘enthalpy of formation’ (more commonly and colloquially called heat of formation) and write this quantity as Hf, instead of the increasingly more commonly used and also proper Hf° and fHm°. No discussion will be made in this chapter on other thermochemical properties such as Gibbs energy, entropy, heat capacity and excess enthalpy. Additionally (following thermochemical convention), the temperature and pressure are tacitly assumed to be 25 °C (‘298 K’) and 1 atmosphere (taken as either 101,325 or 100,000 Pa) respectively3 and the energy units are chosen to be kJ mol 1 instead of kcal mol 1 (where 4.184 kJ 1 kcal, 1 kJ D 0.2390 kcal).

Again, following our earlier chapters as precedent, we continue to view intermolecular forces as ‘complications’ and ‘nuisances’. We consider the molecule per se to be of sole interest and thus, unless explicitly noted to the contrary, any species discussed in this

thermochemistry: ‘Don’t you get bored reading hour after hour, day after day, numbers and their derived problems?’ To which, he responds ‘Yes, and when I do I ask myself ‘Why am I bored?’ and then I have an interesting project’10.

The simplest nonconjugated, acyclic diene is 1,4-pentadiene (1), with its enthalpy of formation of 105.6 kJ mol 1. The obvious question is whether the two double bonds are truly independent. If they are, then the enthalpy of hydrogenation of one double bond as in (the identical) reactions 4a and 4b would be precisely one half of that of the hydrogenation of both as in reaction 5.

would then be thermoneutral. In fact, it is exothermic by merely 1.3 š 2.1 kJ mol 1, a result equal to the expected precise value of 0 within the experimental error bars.

We now turn to the isomeric hexadienes, of which three species qualify for consideration: the 1,5- and the (Z)- and (E)-1,4- compounds, species 13, 14 and 15, respectively. If interaction between the two double bonds in 1,4-pentadiene is so small, we expect this as well for the 1,5-hexadiene. One test of this is to consider reaction 7 by analogy to reaction 6.

CH2DCH(CH2)2CHDCH2 C CH3CH2 CH2 2CH2CH3 !2CH3CH2(CH2)2CHDCH2

7

To do so, one can take the enthalpy of formation of n-hexane from Pedley, and with the phase independence assumptions in Reference 7, employ the enthalpies of hydrogenation of 1-hexene and 1,5-hexadiene from References 11 and 12 respectively. Alternatively13, one can forget about the first quantity altogether and simply take the difference of the enthalpies of hydrogenation of the diene and twice that of the monoene. This reaction is endothermic by 1.1š 1.8 kJ mol 1, a value statistically indistinguishable from the absence of any interolefin interaction in the diene. Relatedly, for the isomeric 1,4-hexadienes 14 and 15, equation 8 may be used.

CH3CHDCHCH2CHDCH2 C CH3 CH2 4CH3 ! CH3CHDCH(CH2)2CH3

C CH3(CH2)3CHDCH2 (8)

Again, one may take the difference of the enthalpies of hydrogenation of the diene and the sum of those for the two monoenes. Doing this separately for 14 and 15, we find the reaction enthalpies for the Z- and E-dienes are 1.9 š 1.2 and 1.8 š 1.1 kJ mol 1. These values are effectively zero. A stabilizing or destabilizing interaction was not expected for nonconjugated acyclic dienes and none was found.

B. Acyclic, Polymeric Polyenes

In this section we will discuss the thermochemistry of a collection of polymeric species of the generic repeat or monomeric formula [ CHDCH (CH2)n 2 ]. We admit that the state of many of the compounds at 298 K is ambiguous, or more precisely, that the sample’s degree of crystallinity (cf the polymer chemist’s terms ‘amorphous solid’ or even vaguer ‘highly elastic’) is ill-defined. As such, any attempts to correct for intermolecular interactions are suspect. We recall that it is easier to predict enthalpies of vaporization than of sublimation, and so conclude that general predictions for liquids are more reliable than for solids. As such, we will study the polymer in its liquid state even if the relevant temperature is not 298 K. No temperature corrections will be made and, given all of the above uncertainties, it seems an unnecessary additional effort to concern ourselves with the precise Z/E composition of the polymer14. The desired numbers in this section are enthalpies of hydrogenation and the final products are n/2 moles of polyethylene, i.e. (CH2CH2)poly, with its derived enthalpy of formation15 of ca52 kJ mol 1.

Starting with the n D 4 case, the desired polymer can be obtained by polymerization of either cyclobutene (16, n D 4) or butadiene. Using the cyclobutene polymerization enthalpy from Reference 16 and of the enthalpy of formation of monomer from Pedley,

[ CHDCH (CH2)3 ] is found to be 14 kJ mol 1. The enthalpy of hydrogenation

121 kJ mol 1. Except for the n D 6 case, the various enthalpies of hydrogenation are around 120 kJ mol 1, a value comparable to those found for numerous simple internal olefins reported in References 11 and 14. We can think of no reason why the n D 6 case should be so different from the others17.

III.CUMULATED OR ALLENIC DIENES AND POLYENES (CUMULENES) A. Allene

We start with a discussion of allene (propadiene), the simplest diene of all. Its gas phase enthalpy of formation is 190.5 š 1.2 kJ mol 1. We wish to compare this quantity with that of related monoenes. The first comparison addresses the ‘relative stability’ of one and two double bonds in a 3-carbon chain. Conceptually, this may be expressed as the enthalpy of the formal reaction 9

2MeCHDCH2 ! C3H8 C CH2DCDCH2 9

We find that allene is destabilized by ca 46 kJ mol 1. Is this destabilization also found for other species with cumulated, or allenic, double bonds?

B. Dienes

Let us start with 1,2-butadiene. A particularly simple analysis is the comparison of allene and 1,2-butadiene using the formal methylation reaction 10

This reaction has an accompanying endothermicity of ca 4 kJ mol 1. Said differently, methylation of ethylene is some 4 kJ mol 1 more exothermic than of allene. How general is this greater exothermicity of alkylation of monoolefins over that of related allenes? Proceeding to the three cumulated 5-carbon dienes, we may consider the reactions

Using standard references and protocol, we find the three reactions are respectively endothermic by ca 2, 8 and 6 kJ mol 1, or ca 2, 4 and 3 kJ mol 1 once one remembers to divide by 2 the last two numbers because the allene is dialkylated. So doing, from equations 10 and 11 we find an average ca 3 kJ mol 1 (per alkyl group) lessened stability for alkylated allenes than the correspondingly alkylated alkenes. This is a small difference that fits most naturally in the study of substituted cumulenes such as ketenes and ketenimines, i.e. not in this chapter. But it is also a guideline for the understanding of polyenes with more cumulated double bonds.

C. Trienes

The thermochemistry of totally cumulated trienes, i.e. species with the CDCDCDC substructure, is very limited. Indeed, the sole examples we know are those reported by Roth, namely (Z)- and (E)-2,3,4-hexatrienes MeCHDCDCDCHMe, species 17 and 18. Their enthalpies of formation are identical to within experimental error, 265 kJ mol 1. This equality is altogether reasonable given the small MežžžMe interaction across the 4- carbon, linear, cumulene chain in contradistinction to the 4.3 kJ mol 1 difference that is found for the isomeric (Z)-and (E)-2-butenes with their significantly smaller MežžžMe distance. Are cumulated trienes ‘unstable’ relative to cumulated dienes much as cumulated dienes are unstable relative to simple olefins? Briefly regressing to cumulated dienes, this assertion is corroborated by the finding that species 3, i.e. 1,3-dimethylallene, has an enthalpy of ‘decarbonization’18 of 144.5 kJ mol 1 (reaction 12)

while the related reactions 13 of the two monosubstituted (R D Me and Et) and the unsubstituted allene (R D H)

TABLE 1. Enthalpies of formation of bis-allenes, the related bis-olefins and bis-acetylenes and their acyclic analogs

a The necessary enthalpy of formation of Me2C (CHDCH2)2 was derived by assuming the reaction Me2CEt2 C CH2 CHDCH2 2 ! Me2C CHDCH2 2 C CH2Et2 is thermoneutral.

b The liquid phase enthalpy of formation of this species is from Pedley; the necessary enthalpy of vaporization was estimated.

found to be ca 130 kJ mol 1. Considering all of the above uncertainties and the relatively exotic structure of 25, we conclude that the bis-allene 25 is not so strange after all21.

IV. CONJUGATED ACYCLIC DIENES

A. Consequences of Conjugation

It is part of the folklore of organic chemistry that the conjugated 1,3-butadiene, 32, enjoys stabilization beyond that were there no interaction between the two double bonds. Indeed, conjugated dienes represent an archetypical example for organic chemists when discussing resonance stabilization accompanying the interaction of two functional groups, and so it may be argued that a new functional group arises.

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What is relevant to this chapter is that a conjugated diene has higher thermodynamic stability than one would expect in the absence of conjugation. Leaving off all hydrogens and substituents in the name of simplicity, several interrelated definitions that document

this stabilization are apparent. The first compares the enthalpy of hydrogenation corresponding to total saturation of the diene; cf reaction 15a with the hydrogenation enthalpies of the related monoenes, cf reactions 15b and 15c. The difference of the first enthalpy,Hr (equation 15a), and the sum of the second and third [ Hr(equation 15b) C Hr (equation 15c)], provides a definition for the conjugation energy, E16 (equation 16).

We immediately recognize this quantity (E16) as equal to the exothermicity of reaction 17:

The result for 1,3-butadiene is 15.7 š 1.9 kJ mol 1, a value comparable to conventional expectations save the sign22. We can now define the difference of the value for an arbitrary conjugated diene of interest and this 15.7 kJ mol 1 as E18 (equation 18).

That is, we can compare the ‘new diene’ with the archetypical 1,3-butadiene where a positive number suggests that it is more stabilized than the paradigm.

The above definition of the enthalpic effects of conjugation is not unique. A second definition decouples the two double bonds by an alternative hydrogenation process (equation 19).

It is found that this reaction, more properly called a hydrogenolysis than a hydrogenation, is only ca 5 kJ mol 1 exothermic for simple species such as 1,3-butadiene and its mono and dimethylated derivatives12,23,24. This is surprisingly close to thermoneutrality. Nonetheless, we have decided to define E20 by equation 20,

where 5.1 š 1.2 kJ mol 1 is the precise hydrogenolysis value for 1,3-butadiene. Again, comparison can be made with 1,3-butadiene where a positive number for E20 implies the new diene is more stable than the archetype. A third definition totally hydrogenates the diene to the saturated hydrocarbon (cf equation 15a), and the difference of this enthalpy and that for the unsubstituted butadiene results in E21 (equation 21):

In this equation the 225.7š 1.3 kJ mol 1 is the hydrogenation enthalpy of 1,3-butadiene to n-butane. This last expression speaks to substituent/diene interactions and to substituent substituent interactions. Both electronic and steric effects contribute. Again, this allows calibration of a substituted diene with 1,3-butadiene itself. A positive sign can be interpreted as the substituted species being more stabilized than the archetype.