π‐Excess Aromatic σ2P Ligands: Formation of a Heterocyclic 1,2‐Diphosphine by the Addition of tBuLi and Subsequent Inverse Addition of the Product at the P=C Bonds of Two Molecules of 1‐Neopentyl‐1,3‐benzazaphosphole

The reactivity of tBuLi (pentane) toward the N‐neopentyl‐substituted π‐excess P=CH–N heterocycle 1 depends on the solvent (tetrahydrofuran, diethyl ether, hexane, and toluene) and reaction conditions. Trapping of the resulting organolithium compounds with CO₂/ClSiMe₃, ClSiMe₃, or EtI led to various products indicating CH lithiation ( 1a , b ), normal addition of tBuLi at the P=C bond (E/Z ‐2a , b ), inverse addition of the primary addition product 2_Li at the P=C bond of a second molecule 1 , affording 3‐tert‐butyl‐2,2’‐bis(1,3‐benzazaphospholines) 3 , or inverse addition of tBuLi ( 4b,c ). The formation of 3 demonstrates a novel route to asymmetric heterocyclic 1,2‐diphosphine ligands. The structure elucidation of the new compounds is based on their ³¹P and ¹³C NMR data with conclusive chemical shifts and P–C coupling constants, that of the isolated PH‐functionalized diphosphine 3 on crystal structure analysis.