We have developed 7-phospha-dibenzonorbornadiene compounds as phosphinidene transfer reagents. With pi-donating diorganoamino substituents at phosphorus, mechanistic studies are consistent with thermal fragmentation of the molecular precursor and transfer to olefin or 1,3-diene acceptors via the free singlet aminophosphinidene. Efforts to identify such molecules in the gas phase will be described. When the substituent at phosphorus is not pi-donating, as in the case of a simple alkyl substituent, thermal fragmentation is not facile, correlating with the observation that such substituents give rise to phosphinidenes having a triplet ground state, in contrast to the aminophosphinidene class. A ruthenium complex of a tetra-pyrrolide macrocycle, first reported by Floriani and coworkers, is found to react with the phosphinidene transfer reagents to produce new ruthenium phosphinidene complexes. This reaction is facile regardless of the nature of the substituent at phosphorus. Efforts to understand and to harness for synthetic utility phosphinidene transfer to styrene, resulting in new phosphirane product molecules by analogy with olefin epoxidation or aziridination, and effected by the ruthenium complexes, will be described.

Phosphinidene chemistry stemming from anthracene-based reagents

255th National Meeting (2018)

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