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Abstract Reaction of Tl(OTf) with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in THF results in formation of [Tl(BAC)₂(OTf)] (1) in moderate yields. Subsequent reaction of1with [K][H₂‐9‐BBN] ([H₂‐9‐BBN]⁻ = dihydrido 9‐boratabicyclo[3.3.1]nonane) in THF results in formation of [Tl(BAC)(μ‐H₂‐9‐BBN)]₂(3), also in moderate yield. Complex3is the first reported thallium borohydride. We attribute its thermal stability to the strong donor ability of the BAC co‐ligand. Both1and3exhibit trigonal pyramidal geometries about Tl⁺in the solid‐state, indicative of the presence of stereochemically active lone pairs. The hydride environment in3is calculated to exhibit a 3.9 ppm downfield shift attributed to spin‐orbit effects from the adjacent Tl center. 

Organometallic cerium(iv) and thorium(iv) alkynyl complexes were synthesized, and compared experimentally and theoretically. A cerium(iv)trans-influence ligand series was observed and analyzed. 

Abstract This computational study explores the copper (I) chloride catalyzed synthesis of (E)‐1‐(2,2‐dichloro‐1‐phenylvinyl)‐2‐phenyldiazene (2Cl‐VD) from readily available hydrazone derivative and carbon tetrachloride (CCl₄).2Cl‐VDhas been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) andN¹,N¹,N²,N²‐tetramethylethane‐1,2‐diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand‐free (LF) route for the removal of a chlorine atom to form the radical·CCl₃but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)‐TMEDA complex catalyzed pathway.