Thermochemistry of the Smallest Hyperbolic Paraboloid Hydrocarbon: A High-Level Quantum Chemical Perspective

[5.5.5.5]hexaene is a [12]annulene ring with a symmetrically bound carbon atom in its center. This is the smallest hydrocarbon with a hyperbolic paraboloid shape. [5.5.5.5]hexaene and related hydrocarbons are important building blocks in organic and materials chemistry. For example, penta-graphene-a puckered 2D allotrope of carbon-is comprised of similar repeating subunits. Here, we investigate the thermochemical and kinetic properties of [5.5.5.5]hexaene at the CCSD(T) level by means of the G4 thermochemical protocol. We find that this system is energetically stable relative to its isomeric forms. For example, isomers containing a phenyl ring with one or more acetylenic side chains are higher in energy by increment ?H-298 = 17.5-51.4 kJ mol(-1). [5.5.5.5]hexaene can undergo skeletal inversion via a completely planar transition structure; however, the activation energy for this process is increment ?H double dagger(298) = 249.2 kJ mol(-1) at the G4 level. This demonstrates the high configurational stability of [5.5.5.5]hexaene towards skeletal inversion. [5.5.5.5]hexaene can also undergo a p-bond shift reaction which proceeds via a relatively low-lying transition structure with an activation energy of increment ?H double dagger(298) = 67.6 kJ mol(-1). Therefore, this process is expected to proceed rapidly at room temperature.

Automated summary

[5.5.5.5]hexaene is a small hydrocarbon with a symmetrically bound carbon atom and a hyperbolic paraboloid shape. It is important in organic and materials chemistry, serving as a building block for structures like penta-graphene. The thermochemical and kinetic properties of [5.5.5.5]hexaene have been investigated, showing its stability and potential reactivity.