As a new means to generate traditionally inaccessible reactive species, we are engaged in the synthesis of well-defined molecular precursors capable of fragmentation at mildly elevated temperatures. Herein, a precursor to phosphaethyne based on extrusion of anthracene and triphenylphosphine will be discussed in terms of its synthesis, characterization, and thermal behavior. Gaseous phosphaethyne evolved from solid samples of the precursor has been analyzed by several spectroscopic techniques, including molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), microwave, and nuclear magnetic resonance (NMR) spectroscopy. In solution, the rate of phosphaethyne generation has been determined by an Eyring analysis, and a mechanism has been elucidated computationally. Phosphaethyne generated in solution this way has been found to undergo a [3+2] cycloaddition reaction with azide to yield the parent 1,2,3,4-triazaphospholate anion, which has been fully characterized. Further work is being done on extending the scope of phosphaalkyne generation to include possible candidates such as phosphacyanogen, NCCP.

Molecular precursor to phosphaethyne: Synthesis, characterization, and further reactivity

251st National Meeting (2016)

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