Some small molecules are stable only under exotic conditions, such as those found in the interstellar medium, or under the conditions of cryogenic matrix isolation. The reaction chemistry of many such molecules is barely explored, despite the fact that their very instability might be exploited in order to achieve new synthetic transformations. Using molecular precursors to facilitate small molecule generation is a tried and true approach for access to reactive intermediates. We have been seeking molecular precursors to P2, PN, HCP, and related molecules, in order to employ them as reactive intermediates in synthetic chemistry for cycloaddition reactions, pathways to metastable materials, or as ligands in transition-metal complexes. In some cases, this has facilitated the synthesis of new small molecules that are stable enough to be isolated, such as AsP3 and HCP3. The relatively recent synthesis and isolation of such molecules, despite their obvious simplicity, illustrates that despite the undeniable sophistication of chemistry as a discipline, many regions of possibility space have yet to be tapped.

Award Address (M. Frederick Hawthorne Award in Main Group Inorganic Chemistry sponsored by the M. Frederick Hawthorne Award Endowment). Small molecule generation

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