A variety of unsymmetric diaryl gold N‐acyclic carbene (NAC) complexes was synthesized via the isonitrile route by three different methods: (a) solvent free in a melt, (b) mechanochemically and (c) in THF at room temperature. The latter method can also be used to synthesize unsaturated gold NHC complexes. These methods overall offer access to a broad array of new complexes and remove one of the previous limitations of the isonitrile route to NAC and NHC complexes of gold, namely the inability to react with the less nucleophilic aromatic amines. The new complexes also proved to be successful as pre‐catalysts in the gold‐catalyzed phenol synthesis.

A flexible [PNP] ligand (forming six-membered chelates upon coordination) was employed for the synthesis of niobium(IV) and tantalum(IV) complexes. Starting from the protioligand (H[PNP]) and the tetrachlorides NbCl4(thf)2 or TaCl4, the trichloro complexes [PNP]MCl3 (1-M, M = Nb, Ta) were prepared via in situ deprotonation using LiN(SiMe3)2. Attempts to alkylate complexes 1-M (M = Nb, Ta), however, were impeded due to their limited solubility in nonchlorinated solvents. Hence, the lithiated ligand was reacted with (thf)2Cl3M=CHCMe2Ph (M = Nb, Ta) to afford the d 0-configured alkylidene complexes 2-Nb and 2-Ta, respectively. These meridionally coordinated and freely soluble complexes were found to be stable in nonchlorinated and chlorinated solvents, even at elevated temperature. Reduction of compounds 2-M with magnesium anthracene (2-Nb and 2-Ta) or sodium naphthalide (2-Ta) afforded the corresponding d 1-configured alkylidenes (3-Nb and 3-Ta), although the reduced niobium derivative was found to decompose rapidly. A 10-line and an 8-line EPR pattern was detected for 3-Nb (I(93Nb) = 9/2) and 3-Ta (I(181Ta) = 7/2), respectively, confirming the metalloradical character of each complex. For 3-Ta, the molecular structure was elucidated by single crystal X-ray diffraction. With the molecular structure of this d 1-configured (open-shell) tantalum alkylidene ascertained, its electronic structure was examined by DFT and CASSCF calculations.

The front cover picture, designed by V. Vethacke, illustrates the four different routes to synthesize unsymmetrically substituted diaryl gold N‐acyclic carbene (NAC) and N‐heterocyclic carbene (NHC) gold complexes via the isonitrile route. The synthesis performed in a melt is depicted as a boiling cauldron, while the mechanochemical one is illustrated as two grinding balls. The synthesis of NAC and NHC complexes in THF at room temperature is illustrated as a wand, since the reaction conditions are surprisingly mild. Details can be found in the Research Article by Hashmi and co‐workers (V. Vethacke, V. Claus, M. C. Dietl, D. Ehjeij, A. Meister, J. F. Huber, L. K. Paschai Darian, M. Rudolph, F. Rominger, A. S. K. Hashmi, Adv. Synth. Catal. 2022, 364, 536–554; DOI: 10.1002/adsc.202101000)