Das Fluor und seine Verbindungen

Moissan, Henri

doi:10.1515/9783112465387

Cited by 13 publications

(11 citation statements)

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“…The study of SF n species began with the synthesis of SF 6 by Moissan in 1900, part of the body of work that was recognized by the 1906 Nobel Prize in chemistry . A thorough review of the experimental and theoretical literature on the structure, spectra, and properties of SF n species is beyond the scope of this work, but we have attempted to compile a reasonably complete bibliography in the Supporting Information for this paper.…”

Section: Introductionmentioning

confidence: 99%

Theory of Hypervalency: Recoupled Pair Bonding in SF_n (n = 1−6)

2009

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To gain new insight into the nature of hypervalency, we have characterized the bonding across the entire SF(n) sequence (n = 1-6) with high-level quantum chemical theory (multireference configuration interaction and coupled cluster calculations using correlation consistent basis sets). In contrast to most previous studies, this work examined both the stable equilibrium structures and the process of SF(n)-F bond formation. We conclude that two different types of bonding can occur in these species: normal polar covalent bonding and a new type that we call recoupled pair bonding. The two bonding processes can be seen in diatomic SF, where hypervalent behavior first occurs. In the covalently bonded (2)Pi ground state, the bond is formed by straightforward singlet coupling of electrons in the singly occupied S 3p and F 2p orbitals. But there is also a low-lying (4)Sigma(-) excited state where the S 3p(2) pair of electrons must first be decoupled so that one of the electrons can singlet couple with the electron in the F 2p orbital, hence the term recoupled pair bonding. Energy is required to decouple the electron pair, but the bond energy of SF((4)Sigma(-)) is still a substantial fraction (about 40%) of the bond energy of SF((2)Pi). Recoupled pair bonding is the basis for hypervalent behavior: for example, the three unpaired electrons of SF((4)Sigma(-)) are available for further bond formation, and their spatial orientations clearly anticipate the structure of SF(4). The new model of hypervalent bonding introduced in this work accounts for the observed trends in the structures of SF(n) molecules and the variations in the (SF(n)-F) bond energies. The model also predicts the existence of low-lying excited states in some SF(n) species and provides explanations for their energetic separations and orderings.

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Section: Introductionmentioning

confidence: 99%

Theory of Hypervalency: Recoupled Pair Bonding in SF_n (n = 1−6)

2009

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“…When available, metal carbides can be converted directly to halides by their reaction with halogens or hydrogen halides at elevated temperatures (76,77,79,80,87). The reactions between lanthanon carbides and a halogen on a hydrogen halide occur in accordance with equations 6 and 7.…”

Section: Introductionmentioning

confidence: 99%

“…Other binary metallic compounds of lanthanons such as the sulfides (78,81,82), nitrides, and hydrides (72) which have been used to prepare anhydrous lanthanon halides offer no special advantage since such compounds usually are not readily available in the pure form. A general method for preparing anhydrous halides from oxides was developed by Oersted (84) in 1824.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Anhydrous Lanthanon Halides.

Taylor¹

1962

Chem. Rev.

119

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“…If the original attack of the benzotrifluoride occurs as shown below, the benzotrifluoride radical produced can react in three <Q>-CF3 + F• -<0>-CF3 + HF <0>-CF• +F' -F-<0>-CF3 ways: (1) with atomic fluorine to produce monofluorobenzotrifluoride; (2) with another benzotrifluoride radical to produce bis(trifluoromethyl)biphenyl; (3) with a benzotrifluoride molecule to initiate polymerization.…”

Section: Discussionmentioning

confidence: 99%