Synthesis, Purification, and Rotational Spectroscopy of (Cyanomethylene)Cyclopropane-An Isomer of Pyridine.

Abstract

The gas-phase rotational spectrum of (cyanomethylene)cyclopropane, (CH2)2C═CHCN, generated by a Wittig reaction between the hemiketal of cyclopropanone and (cyanomethylene)triphenylphosphorane, is presented for the first time. This small, highly polar nitrile is a cyclopropyl-containing structural isomer of pyridine. The rotational spectra of the ground state and two vibrationally excited states were observed, analyzed, and least-squares fit from 130 to 360 GHz. Over 3900 R-, P-, and Q-branch, ground-state rotational transitions were fit to low-error, partial octic, A- and S-reduced Hamiltonians, providing precise determinations of the spectroscopic constants. The two lowest-energy vibrationally excited states, ν17 and ν27, form a Coriolis-coupled dyad displaying small a- and b-type resonances. Transitions for these two states were measured and least-squares fit to a two-state, partial octic, A-reduced Hamiltonian in the Ir representation with nine Coriolis-coupling terms (Ga, GaJ, GaK, GaJJ, Fbc, FbcJ, FbcK, Gb, and GbJ). The observation of many resonant transitions and nine nominal interstate transitions enabled a very accurate and precise energy difference between ν17 and ν27 to be determined: ΔE17,27 = 29.8975453 (33) cm-1. The spectroscopic constants presented herein provide the foundation for future astronomical searches for (cyanomethylene)cyclopropane.