Highly Strained Pn(CH)3 (Pn = N, P, As, Sb, Bi) Tetrahedranes: Theoretical Characterization

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-04, Vol.125 (12), p.2612-2621
• Main Authors: Wolf, Mark E, Doty, Elizabeth A, Turney, Justin M, Schaefer III, Henry F
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c01022

Recent experimental research by Cummins and co-workers has established the existence of a tetrahedrane molecule with one CH moiety replaced by phosphorus. We present here the first theoretical studies of the entire Pn­(CH)3 (Pn = N, P, As, Sb, Bi) class of molecules. Geometries are obtained at the highly reliable CCSD­(T)/aug-cc-pwCVTZ­(-PP) level of theory. Harmonic vibrational frequencies are determined and analyzed to confirm the nature of each stationary point and provide helpful findings that may aid in the detection of each species. Most notable is the result that the geometric parameters associated with the (CH)3 moiety in the tetrahedranes exhibit little change under pnictogen substitution, while the Pn–C bonds and C–Pn–C bond angles greatly increase and decrease, respectively. Strain energies are predicted and range from 122.3 kcal mol–1 (N­(CH)3) to 99.4 kcal mol–1 (Bi­(CH)3) at the DF-CCSD­(T)//B3LYP-D3/aug-cc-pV­(T+d)­Z­(-PP) level of theory. The obtained geometries are further analyzed with Natural Bond Orbital (NBO) methods to understand the bonding and electronic structure of each species. We also provide insight into how different substituents can help make the tetrahedrane structure more energetically favorable due to electron delocalization into substituent antibonding orbitals. The effect of additional delocalization also weakens the Pn–C bonds, especially for the heavier pnictogens. This work concludes with a list of considerations that summarize our key findings and motivate future work aimed at producing novel pnictogen-substituted tetrahedrane molecules.