The Paterno-Buchi reaction: importance of triplet states in the excited-state reaction pathway

TY - JOUR

T1 - The Paterno-Buchi reaction

T2 - importance of triplet states in the excited-state reaction pathway

AU - Brogaard, Rasmus Yding

AU - Schalk, Oliver

AU - Boguslavskiy, Andrey E.

AU - Enright, Gary D.

AU - Hopf, Henning

AU - Raev, Vitaly

AU - Tarcoveanu, Eliza

AU - Sølling, Theis Ivan

AU - Stolow, Albert

PY - 2012/6/28

Y1 - 2012/6/28

N2 - The Paternò-Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity. This journal is

AB - The Paternò-Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity. This journal is

U2 - 10.1039/c2cp40819h

DO - 10.1039/c2cp40819h

M3 - Journal article

C2 - 22614254

SN - 1463-9076

VL - 14

SP - 8572

EP - 8580

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 24

ER -