π bond versus radical character of the diamond (1 0 0)-2×1 surface

The dimers on clean diamond (1 0 0)-2×1 are linked by a σ bond and a highly strained π bond. The weakness of the surface π bond causes the reactivity of this surface to be intermediate between that of an alkene and a bi-radical. We illustrate this behavior by investigating two prototypical cycloaddi...

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Bibliographic Details
Published in:Materials chemistry and physics 2001-11, Vol.72 (2), p.147-151
Main Authors: Russell, John N., Butler, James E., Wang, George T., Bent, Stacey F., Hovis, Jennifer S., Hamers, Robert J., D’Evelyn, Mark P.
Format: Article
Language:English
Subjects:
CVD
Diamond
FTIR
Surface chemistry
Surface modification
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Summary:The dimers on clean diamond (1 0 0)-2×1 are linked by a σ bond and a highly strained π bond. The weakness of the surface π bond causes the reactivity of this surface to be intermediate between that of an alkene and a bi-radical. We illustrate this behavior by investigating two prototypical cycloaddition surface reactions using multiple-internal-reflection infrared spectroscopy. Adsorption of 1,3-butadiene occurs via [4+2] addition to surface dimers, analogous to Diels–Alder chemistry of alkenes. However, [2+2] cycloaddition of cyclopentene, a reaction that is symmetry-forbidden with alkenes, occurred with a sticking coefficient of ∼10 −3. These reactions illustrate novel approaches to the functionalization of diamond surfaces.
ISSN:0254-0584
1879-3312
DOI:10.1016/S0254-0584(01)00425-4