Energetics and kinetics of various cyano radical hydrogen abstractions

Accurate energetics and rate constants have been obtained for various hydrogen abstraction reactions by the cyano radical using highly accurate ab initio methods.

Experimental energy levels of 12C14N through marvel analysis

ABSTRACT The cyano radical (CN) is a key molecule across many different factions of astronomy and chemistry. Accurate, empirical rovibronic energy levels with uncertainties are determined for eight doublet states of CN using the marvel (Measured Active Rotational-Vibrational Energy Levels) algorithm. 40 333 transitions were validated from 22 different published sources to generate 8083 spin-rovibronic energy levels. The empirical energy levels obtained from the marvel analysis are compared to current energy levels from the mollist line list. The mollist transition frequencies are updated with marvel energy level data which brings the frequencies obtained through experimental data up to 77.3 per cent from the original 11.3 per cent, with 92.6 per cent of the transitions with intensities over 10−23 cm molecule−1 at 1000 K now known from experimental data. At 2000 K, 100.0 per cent of the partition function is recovered using only marvel energy levels, while 98.2 per cent is still recovered at 5000 K.

Selective Phthalimido-N-oxyl (PINO)-Catalyzed C–H Cyanation of Adamantane Derivatives

We present a new method for the selective C(sp3)–H cyanation of adamantane derivatives with PINO as the hydrogen abstracting reagent. A cyano radical is thereby transferred from p -toluenesulfonyl cyanide, allowing the cyanation of adamantane derivatives in up to 71% yield. The protocol presents a novel way to orthogonally functionalized adamantanes that are otherwise difficult to prepare. Mechanistic studies support the hypothesis of a radical pathway.

Kinetics study of the CN + CH4 hydrogen abstraction reaction based on a new ab initio analytical full-dimensional potential energy surface

We have developed an analytical full-dimensional potential energy surface, named PES-2017, for the gas-phase hydrogen abstraction reaction between the cyano radical and methane.