On the Basicity of Carboranylphosphines

Amanda Benton, Derek J Durand, Zachariah Copeland, James D Watson, Natalie Fey, Stephen M Mansell, Georgina M Rosair, Alan J Welch

Research output: Contribution to journalArticle (Academic Journal)peer-review

13 Citations (Scopus)
158 Downloads (Pure)


Three new carboranylphosphines, [1-(1′-closo-1′,7′-C2B10H11)-7-PPh2-closo-1,7-C2B10H10], [1-(1′–7′-PPh2-closo-1′,7′-C2B10H10)-7-PPh2-closo-1,7-C2B10H10], and [1-{PPh-(1′-closo-1′,2′-C2B10H11)}-closo-1,2-C2B10H11], have been prepared, and from a combination of these and literature compounds, eight new carboranylphosphine selenides were subsequently synthesized. The relative basicities of the carboranylphosphines were established by (i) measurement of the 1JPSe NMR coupling constant of the selenide and (ii) calculation of the proton affinity of the phosphine, in an attempt to establish which of several factors are the most important in controlling the basicity. It is found that the basicity of the carboranylphosphines is significantly influenced by the nature of other substituents on the P atom, the nature of the carborane cage vertex (C or B) to which the P atom is attached, and the charge on the carboranylphosphine. In contrast, the basicity of the carboranylphosphines appears to be relatively insensitive to the nature of other substituents on the carborane cage, the isomeric form of the carborane, and whether the cage is closo or nido (insofar as that does not alter the charge on the cluster). Such information is likely to be of significant importance in optimizing future applications of carboranylphosphines, e.g., as components of frustrated Lewis pairs.
Original languageEnglish
Pages (from-to)14818-14829
Number of pages12
Issue number21
Early online date22 Oct 2019
Publication statusPublished - 4 Nov 2019


  • Computational chemistry
  • Ligands
  • Synthesis
  • Carborane
  • Analysis


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