A range of λ 3 -phosphaalkynes P⋮C−R (R = F, Cl, O -, OLi, OH, OSiMe 3, S -, SLi, SH, Me, SiMe 3, H) 1 has been geometry-optimized at the HF, MP2, and CCSD(T) level of theory. Vibrational frequencies as well as 31 P and 13 C NMR chemical shifts were calculated and compared to experimental values of the large variety of λ 3 -phosphaalkynes prepared over several years via differing synthetic routes. With a few obvious exceptions, a good agreement of calculated and experimental parameters was found. This also opens up the possibility to make predictions on spectroscopic data of compounds not yet synthesized or fully characterized, e.g., PCOSiMe 3 and PCSH. The bonding situation especially of the negatively charged species P⋮C−O - and P⋮C−S - was studied via NBO analyses to determine the degree of phosphaalkyne and heterocumulene contributions to the mesomeric anions.
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Hübler et al. (1998) studied this question.