Cycloaddition reaction on Si

If the analogy that is drawn between the Si=Si dimer on the Si(100)-2 x 1 surface and an alkene group is reasonable, then certain parallels might be expected to exist between cycloaddition reactions in organic chemistry and reactions that occur between alkenes or dienes and the silicon surface. In other words, cycloaddition products should be observed on the Si(100)-2 x 1 surface. Indeed, this prediction has been borne out in a number of studies of cycloaddition reactions on Si(100)-2x1 [14], as well as on the related surfaces of Ge(100)-2 x 1 (see Section 6.2.1) and C(100)-2 x 1 [192-195]. On the other hand, because the double-bonded description is only an approximation, deviations from the simple picture are expected. A number of studies have shown that the behavior differs from that of a double bond, and the asymmetric character of the dimer will be seen to play an important role. For example, departures from the symmetry selection rules developed for organic reactions are observed at the surface. Several review articles address cycloaddition and related chemistry at the Si(100)-2 x 1 surface the reader is referred to Refs. [10-18] for additional detail. 

The first examples of what can be categorized as [2 + 2] type cycloaddition product formed by reaction between an alkene and a silicon surface were reported in the late 1980s. Alkenes such as ethylene, as well as the related alkyne molecule acetylene, were reacted with the clean Si(100)-2 x 1 surface in vacuum [196-213]. The adsorption of these unsaturated C2 molecules (ethylene and acetylene) on Si(100)-2 x 1 is also discussed in Chapter 1. The alkenes were found to chemisorb at room temperature, forming stable species that bridge-bonded across the silicon dimers on the surface. The reaction proceeded by formation of two new a bonds between Si and C atoms, hence the bonding was referred to as di-sigma bonding. In addition, it was shown that while the bonds of the alkene and of the Si—Si dimer are 

Ordered overlayers are not achieved in all systems, however, and it appears that certain criteria need to be met to form well-ordered films. Although cyclopentene and 1,5-cyclooctadiene could be used to produce ordered monolayer films through [2 + 2] attachment [221], a number of other alkenes investigated did not adsorb 

Alkynes have also been shown to form the [2 + 2] cycloaddition product. Acetylene (H—C=C—H), the simplest alkyne, forms an interesting adsorption case, because the specific adsorption geometries of acetylene on Si(100)-2 x 1 have been debated [11,201,207,210,224-236]. Acetylene was first found experimentally to form a [2 + 2] C=C cycloaddition product that exhibits a cyclobutene-like surface structure on Si(100)-2 x 1 [210,227]. Later STM measurements revealed that at least two different surface products were present [228,231,233], and identified a product that is oriented perpendicularly to the dimer row. From these images, it was argued that in addition to an intradimer [2 + 2] C=C cycloaddition geometry, acetylene also forms a surface adduct that bridges two dimers along a row. Several theoretical 

[4 + 2] Cycloadditions, or Diels-Alder reactions, on silicon The other common type of cycloaddition reaction in organic chemistry is the [4 + 

---

A recent theoretical study has nicely addressed the question of mechanism on the silicon surface. Minary and Tuckerman carried out an ab initio molecular dynamics (MD) study of the [4 + 2] cycloaddition reaction on Si(100)-2 x 1 [251]. Because the previously reported ab initio DFT models were static , these were not able to address in detail the mechanisms by which the [4 + 2] product was formed. The results of the MD study indicate that rather than being concerted, the dominant mechanism is a stepwise zwitterionic process in which an initial nucleophilic attack of one of the C=C bonds by the down atom of the dimer leads to a carbocation. This carbocation exists for up to 1-2 ps, stabilized by resonance, and depending on which positively charged carbon atom reacts with which Si surface atom, can form... 

---