Synthetic and Spectroscopic Investigations Enabled by Modular Synthesis of Molecular Phosphaalkyne Precursors

摘要

A series of dibenzo-7-phosphanorbornadiene compounds, Ph3PC(R)PA (1-R; A = C14H10, anthracene; R = Me, Et, Pr-i, Bu-s), are reported to be capable of thermal fragmentation to generate alkyl-substituted phosphaalkynes (RC P) concomitant with triphenylphosphine and anthracene. Facile preparation of these molecular precursors proceeds by treatment of ClPA with the appropriate ylide Ph3P=CHR (2 equiv). For methyl, ethyl, and isopropyl substituents, the phosphaalkyne conversions are measured to be 56-73% in solution by quantitative P-31 NMR spectroscopy. In the case of compound 1-Me, the kinetic profile of its spontaneous unimolecular fragmentation is investigated by an Eyring analysis. The resulting 1-phosphapropyne is directly detected by solution NMR spectroscopy and gas phase rotational microwave spectroscopy. The latter technique allows for the first time measurement of the phosphorus-31 nuclear spin-rotation coupling tensor. The nuclear spin-rotation coupling provides a link between rotational and NMR spectroscopies, and is contextualized in relation to the chemical shift anisotropy.