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Abstract

Diphenylcarbene (DPC) shows a triplet ground-state lying approximately 3 kcal/mol below the lowest singlet state. Under the conditions of matrix isolation at 25 K, DPC reacts with single water molecules embedded in solid argon and switches its ground state from triplet to singlet by forming a strong hydrogen bond. The complex between DPC and water is only metastable, and even at 3 K the carbene center slowly inserts into the OH bond of water to form benzhydryl alcohol via quantum chemical tunneling. Surprisingly, if DPC is generated in amorphous water ice at 3 K, it is protonated instantaneously to give the benzhydryl cation. Under these conditions, the benzhydryl cation is stable, and warming to temperatures above 50 K is required to produce benzhydryl alcohol. Thus, for the first time, a highly electrophilic and extremely reactive secondary carbenium ion can be isolated in a neutral, nucleophilic environment avoiding superacidic conditions.