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Article

Theoretical Study of the Addition Patterns of C₆₀ Fluorination: C₆₀F_n (n = 1−60)

Supporting Info

Gregory Van Lier,^†^‡ Montserrat Cases,^§^‡ Christopher P. Ewels, Roger Taylor,^# and Paul Geerlings*^‡

Unit de Physico-Chimie et de Physique des Matriaux (P.C.P.M.), Universit catholique de Louvain (UCL), Place Croix du Sud, 1 (Boltzmann), B-1348 Louvain-la-Neuve, Belgium; Research Group of General Chemistry (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050, Brussels, Belgium; Institut de Qumica Computacional and Departament de Qumica, Universitat de Girona, E-17071 Girona, Catalonia, Spain; Composite Systems and Materials Department (DMSC), ONERA BP72, 29 Avenue de la Division Leclerc, 92322 Chatillon, France; Laboratoire de Physique des Solides (LPS), Universit Paris Sud, Batiment 510, 91405 Orsay, France; and Chemistry Department, University of Sussex, Falmer, Brighton BN1 9QJ, United Kingdom

J. Org. Chem., 2005, 70 (5), pp 1565–1579

DOI: 10.1021/jo0483872

Publication Date (Web): February 4, 2005

†

Université catholique de Louvain.

‡

Vrije Universiteit Brussel.

Universitat de Girona.

ONERA.

Université Paris Sud.

University of Sussex.

To whom correspondence should be addressed. Phone: +32.2. 629.33.14. Fax: +32.2.629.33.17.

, pgeerlin@vub.ac.be

Abstract

A systematic study is presented of addition patterns occurring upon fluorination of C₆₀. We use the program SACHA, which increments the number of fluorine addends, tests all available addition sites within a given cutoff radius, and selects the most energetically stable structure for further addition on the basis of full AM1 optimizations for every isomer. The lowest energy structures are optimized at HF/3-21G level of theory. A number of distinct addition routes are predicted, based on octahedral, ‘S', and ‘T' addition patterns, leading both to experimentally observed C₆₀F_n isomers and to isomers not previously described in the literature. Furthermore the main addition routes were analyzed for C₆₀F₂_n isomers, using ab initio global and local aromaticity calculations. For this, magnetizability and NICS calculations have been carried out at HF/3-21G level of theory. We show the possibility of using NICS to predict the next preferential addition site, matching the above-described addition routes.

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