Abstract

The rotational spectra of the four isotopomers (CH 3) 3P⋯HF, (CH 3) 3P⋯DF, (CH 3) 2( 13CH 3)P⋯HF and (CD 3) 3P⋯HF of a hydrogen-bonded complex formed by trimethylphosphine and hydrogen fluoride have been observed by pulsed-nozzle Fourier-transform microwave spectroscopy. The H, F nuclear spin–spin coupling constant D HF aa and the D-nuclear quadrupole coupling constant χ D aa were determined for the first two isotopomers. Interpretation of these coupling constants in conjunction with rotational constants and centrifugal distortion constants allows the conclusion that the intermolecular binding is relatively weak ( k σ =17.2(3) N m −1), with only a small lengthening δ r≈0.012 Å of the HF bond on formation of a symmetric-top complex (CH 3) 3P⋯HF having r(P⋯F)=3.120(2) Å.

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