Dibenzo-7-phosphanorbornadiene Ph3PC-(H)PA (1, A = 14 C- H-10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of Delta H-double dagger = 25.5 kcal/mol and Delta S-double dagger =-2.43 eu and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high-temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3-, for which structural data have been obtained in a single-crystal X-ray diffraction study. Negative-ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3- has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.