Tom Mastrangelo

B.A. Cornell University (2004)

Likes: chicken parm, 90's rap, PlayStation, cation radicals

Dislikes: beets, cigarrette smoke, anion radicals

Tom hails from the small town of Lyons, NY, peppermint capitol of the world. Since childhood he has had a devout curiosity about the way things work, and as a right-brained individual, physical organic chemistry was a natural choice of study. Although college saw him dabble in art and theater, there was never a doubt where he was headed after graduation.

Tom's research aims to elucidate the mechanisms by which silane cation radicals react with nucleophiles. In particular, because of the presence of accessible d orbitals on silicon, silyl cation radicals are capable of conjugative stabilization through silicon-silicon single bonds. This tends to stabilize the cation radical as additional silicon atoms are added to the chain, resulting in a higher transition state barrier. Thus nucleophile rate constants are mitigated.

Cation/anion radical pairs are typically generated through photo-induced charge transfer, a process where light is absorbed by a molecule, causing the donation of an electron from the excited state molecule to a ground state recipient. Hopefully the ion radicals will diffuse apart and rapidly perform interesting chemistry. It is interesting to note the reactive sites of tri and tetrasilane cation radicals. Do these ruthless electrophiles cleave bimolecularly at a terminal silicon or an internal one? We hope to chromatographically observe if the products of the bimolecular cleavage reactions fit our expectations of relative bond dissociation energies. Sorting through the potential hodgepodge of side reactions would be feasible if we could force the anion radical to eradicate stray silyl radicals via a one electron redox reaction. This is not trivial, as such a feat would require exceptional experimental design.

Stupid anion radicals. They think they can do whatever they want.