Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides

Abstract

A series of unique C₂P₃-ring compounds [(ADC^Ar)P₃] (ADC^Ar = ArC{(DippN)C}₂; Dipp = 2,6-iPr₂C₆H₃; Ar = Ph 4a, 3-MeC₆H₄4b, 4-MeC₆H₄4c, and 4-Me₂NC₆H₄4d) are readily accessible in an almost quantitative yield by the direct functionalization of white phosphorus (P₄) with appropriate anionic dicarbenes [Li(ADC^Ar)]. The formation of 1,2,3-triphosphol-2-ides (4a–4d) suggests unprecedented [3 + 1] fragmentation of P₄ into P₃⁺ and P⁻. The P₃⁺ cation is trapped by the (ADC^Ar)⁻ to give 4, while the putative P⁻ anion reacts with additional P₄ to yield the Li₃P₇ species, a useful reagent in the synthesis of organophosphorus compounds. Remarkably, the P₄ fragmentation is also viable with the related mesoionic carbenes (iMICs^Ar) (iMIC^Ar = ArC{(DippN)₂CCH}, i stands for imidazole-based) giving rise to 4. DFT calculations reveal that both the C₃N₂ and C₂P₃-rings of 4 are 6π-electron aromatic systems. The natural bonding orbital (NBO) analyses indicate that compounds 4 are mesoionic species featuring a negatively polarized C₂P₃-ring. The HOMO−3 of 4 is mainly the lone-pair at the central phosphorus atom that undergoes σ-bond formation with a variety of metal-electrophiles to yield complexes [{(ADC^Ar)P₃}M(CO)_n] (M = Fe, n = 4, Ar = Ph 5a or 4-Me-C₆H₄5b; M = Mo, n = 5, Ar = Ph 6; M = W, n = 5, Ar = 4-Me₂NC₆H₄7).