Configurational Stability of Chlorophosphines

Configurational Stability of Chlorophosphines

The configurational stability of chlorophosphines is investigated. Several mechanisms involving chlorophosphine monomer, dimers, and adducts with HCl are evaluated by density functional theory calculations. The presence of HCl in the medium is found to catalyze the P-center chiral inversion at room...

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Veröffentlicht in:Inorganic chemistry 2003-01, Vol.42 (2), p.420-427
Hauptverfasser: Humbel, Stéphane, Bertrand, Cyrille, Darcel, Christophe, Bauduin, Christophe, Jugé, Sylvain
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Theoretical and
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container_end_page 427
container_issue 2
container_start_page 420
container_title Inorganic chemistry
container_volume 42
creator Humbel, Stéphane
Bertrand, Cyrille
Darcel, Christophe
Bauduin, Christophe
Jugé, Sylvain
description The configurational stability of chlorophosphines is investigated. Several mechanisms involving chlorophosphine monomer, dimers, and adducts with HCl are evaluated by density functional theory calculations. The presence of HCl in the medium is found to catalyze the P-center chiral inversion at room temperature. The reaction involves a two-step mechanism with low transition states (10 kcal·mol-1) and a stabilized achiral intermediate (−2.6 kcal·mol-1). Further calculations and experiments on the halogen exchange with HBr corroborate this mechanism, with bromophosphines being formed instantaneously. Finally, to avoid the racemization, the borane is found to be a very promising protecting group for the configurational stability of the P-chirogenic chlorophosphines.
doi_str_mv 10.1021/ic026128u
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title Configurational Stability of Chlorophosphines
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