Preparation of a potassium chloride bridged thorium phosphinidiide complex and its reactivity towards small organic molecules

The KCl-bridged phosphinidiide thorium metallocene, {[eta(5)-1,3-(Me3C)(2)C5H3](2)Th(xe001;P-2,4,6-(Pr3C6H2)-Pr-i)(ClK)}(2) (2), was isolated in good yield by a salt metathesis reaction of the thorium methyl chloride compound [eta(5)-1,3-(Me3C)(2)C5H3](2)Th(Cl)Me (1) with 2,4,6-(Pr3C6H2PHK)-Pr-i in toluene. Furthermore, it was fully characterized including its molecular structure. The reactivity of 2 towards various small organic molecules was also explored, e.g., it reacts with alkynes, nitriles, CS2, quinolines, silanes, pyridine and imidazole derivatives, resulting in metallacycles, imidos, carbodithiolates, and phosphido compounds. Density functional theory (DFT) computations were conducted to supplement the experimental investigations.