Understanding and quantifying the electronic properties of ligands is important both from a fundamental point of view and also for their applications in various branches of chemistry. In this contribution, we present a comparative study on the donor/acceptor properties of 10 different triazolylidene-type mesoionic carbene ligands (MICs), with the aim of investigating and deciphering the effects of substituents on the donor/acceptor properties of such MIC ligands. Data from 77Se NMR chemical shifts of the triazoline selones, the 1 J C‑H coupling constants of the corresponding triazolium salts, and the Tolman electronic parameters (TEP) of the Ir-CO complexes are compared and contrasted. The data collected in this work show that the spread of both the TEP and the 1 J C‑H coupling constants is relatively narrow to be able to significantly differentiate between the donor properties of the various MICs. The 77Se NMR shifts of the triazoline selones on the other hand show a broad spread, and it is in principle well-suited to understand the π-accepting properties of the MICs as a function of substituents. However, this method can have other complications which are discussed in this work. DFT calculations are presented to spread light on the 77Se NMR shifts. Additionally, we present the first example of a AuI complex with mesoionic triazoline selones, a class of ligands whose utility has remained underexplored in transition metal chemistry.

We present a modular, synthetic entry to polysubstituted pyrroles employing readily available 2,5-dihydrothiophenes. Ring-opening of the heterocycle provides access to a panel of 1,3-dienes which undergo pyrrole formation in the presence of inexpensive chloramine-T trihydrate. The transformation is conducted in an open flask and proceeds at ambient temperatures (23 °C) in nondry solvents. A careful adjustment of the electronics and sterics of the 1,3-diene precursor allows for the isolation of key intermediates. DFT studies identified a reaction mechanism that features a 6π-electrocyclization of a sulfilimine intermediate followed by spontaneous ring-contraction to reveal the pyrrole skeleton.