Group 15 And 16 Nitrene-Like Pnictinidenes

Pnictinidenes are an increasingly relevant species in main group chemistry and generally exhibit proclivity for the triplet electronic ground state. However, the elusive singlet electronic states are often desired for chemical applications. We predict the singlet-triplet energy differences (Delta E-ST=E-Singlet-E-Triplet) of simple group 15 and 16 substituted pnictinidenes (Pn-R; Pn=P, As, Sb, or Bi) with highly reliable focal-point analyses targeting the CCSDTQ/CBS level of theory. The only cases we predict to have favorable singlet states are P-PH2 (-3.2 kcal mol(-1)) and P-NH2 (-0.2 kcal mol(-1)). Delta E-ST trends are discussed in light of the geometric predictions as well as qualitative natural bond order analysis to elucidate some of the important electronic structure features. Our work provides a rigorous benchmark for the Delta E-ST of fundamental Pn-R moieties and provides a firm foundation for the continued study of heavier pnictinidenes.