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On the Edge of the Known: Extremely Electron-Rich (Di)Carboranyl Phosphines.

Jan SchulzReike ClaussAleksandr KazimirSieglinde HolzknechtEvamarie Hey-Hawkins
Published in: Angewandte Chemie (International ed. in English) (2022)
The syntheses of the first B9-connected carboranylphosphines (B9-Phos) featuring two carboranyl moieties as well as access to B9-Phos ligands with bulky electron-donating substituents, previously deemed unattainable, is reported. The electrochemical properties of the B9-Phos ligands were investigated, revealing the ability of the mesityl derivatives to form stabilized phosphoniumyl radical cations. The B9-Phos ligands display an extremely electron-releasing character surpassing that of alkyl phosphines and commonly used N-heterocyclic carbenes. This is demonstrated by their very small Tolman electronic parameters (TEPs) as well as extremely low P-Se coupling constants. Cone angles and buried volumes attest to the high steric demand exerted by the (di)carboranyl phosphines. The dicarboranyl phosphine Au I complexes show superior catalytic performance in the hydroamination of alkynes compared to the monocarboranyl phosphine analogs.
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