Nguyen Minh Tho, Spasyuk Denis, White Brandon, Dudding Travis, Nikonov Georgii I
Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario L2S 3A1, Canada.
SM and MX Crystallography, Canadian Light Source Inc., 44 Innovation Blvd., Saskatoon, Saskatchewan S7N 2V3, Canada.
Dalton Trans. 2021 Nov 23;50(45):16613-16619. doi: 10.1039/d1dt03181c.
Reduction of phosphorus dichloride 6, supported by the diaryloxyphenyl group (OCO) featuring two bulky phenoxy wingtips, by PMe, generates a reactive intermediate that behaves as a base-stabilized phosphinidene (OCO)P (5). Warming up a solution of this species in toluene to room temperature results in trimerization to give the isolable cyclic triphosphine [(OCO)P], whereas trapping with 2,3-dimethylbutadiene-1,3 afforded a 3,4-dimethylphospholene-3. Investigation of the reduction of 6 by the phosphine PMe by NMR led to the observation of a persistent species between -10 °C and 10 °C. A DFT study of this process suggests that this compound cannot be the proposed phosphinidene 5, and is more likely the diphosphine (OCO)ClP-PCl(OCO) (12). Attempted reduction of 5 by the bulky carbene IPr resulted in unusual electrophilic substitution in the carbene olefin backbone by the chlorophosphinyl group.
