Group 15 and 16 Nitrene‐Like Pnictinidenes. Issue 58 (15th September 2021)

• Record Type: Journal Article
• Authors: Mitchell, Erica C.; Wolf, Mark E.; Turney, Justin M.; Schaefer, Henry F.
• Is Part Of: Chemistry. Volume 27:Issue 58(2021)
• Page Start: 14461
• Page End: 14471
• Publication Date: 2021-09-15
• Subjects: ab initio calculations -- electronic structures -- Lewis bases -- ligand effects -- phosphorus; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202101832
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 (ΔEST =ESinglet −ETriplet ) 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 ). ΔEST 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 ΔEST of fundamental Pn−R moieties and provides a firm foundation for the continued study of heavier pnictinidenes. Abstract : Singlet‐triplet gap energies are computed for simple pnictinidene moieties to offer theoretical insights and motivate future work on heavier pnictogen containing species.