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 ¹J_PSe 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.

Zachariah Copeland

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