Insight into fragmentation of a phosphirane to form phosphinidene complexes: an illustration with the 1-phenylselenylphosphirane W(CO)5 complex

Density functional theory (DFT) calculations with 1-phenylselenyl-phosphirane complex 1 provide an insight into phosphirane fragmentation to phosphinidene complexes. FMO and ELF analyses show that the cleavage of two P-C sigma bonds of phosphirane proceeds via an asynchronous concerted pathway. Transient [PhSeP-W(CO)(5)] was generated by dissociation of 1 at 90 degrees C and trapped with different reagents. The 1-phenoxylphosphirane complex undergoes [1 + 2] retroaddition at a comparatively higher temperature which implies that the lone pair of the adjacent atom center of phosphorus plays a major role in phosphirane fragmentation.

Automated summary

Density functional theory calculations were used to investigate the fragmentation mechanism of 1-phenylselenyl-phosphirane complex. The results reveal that the reaction proceeds via an asynchronous concerted pathway, with the lone pair of the adjacent phosphorus atom playing a crucial role in the process.