Structural and Stereochemical Applications of Computational NMR Using²⁹Si-¹H and⁷⁷Se-¹H Indirect Spin-Spin Coupling Constants

Computational NMR of Carbohydrates: Theoretical Background, Applications, and Perspectives

“…A number of recent comprehensive reviews concentrated on particular computational aspects for the less common nuclei (i.e., those excluding 1 H and 13 C)-namely, nitrogen [27], fluorine [28], silicon [29], phosphorus [30,31], selenium [32][33][34], and heavy nuclei [34][35][36]. Theoretical calculations of NMR parameters are nowadays performed at either non-empirical (ab initio) level with taking into account electronic correlation in an explicit way or within the density functional theory (DFT) including electronic correlation effects inexplicitly.…”

“…Figure32. Structural differences of heparin chains associated with distinct conformations of iduronic acid residues.…”

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

“…In this respect, a delicate approach is required for the calculation of the indirect nuclear spin-spin coupling constants (SSCCs) involving selenium [29][30][31][32] because the calculation of the SSCCs with heavy chalcogens from the fourth period and below, in general, represents a challenging task [33][34][35][36][37][38][39][40][41] due to the complexity of the electronic structure of such systems and the need to pay special attention to the relativistic effects [42][43][44][45]. Accurate computation of the selenium SSCCs covers a wide range of applicability, representing, in the first place, a powerful tool of the stereochemical studies of organoselenium compounds [46][47][48][49][50][51][52][53][54]. Indeed, it should be emphasized that Se-H and Se-C SSCCs manifest a pronounced stereochemical 2 of 18 behavior basically governed by the orientational lone-pair effect of selenium [48,55].…”

Quantum chemical calculations of77Se and125Te nuclear magnetic resonance spectral parameters and their structural applications

“…Recent advances in selenium and tellurium NMR spectroscopy are covered in a great number of comprehensive reviews, [26][27][28][29][30][31][32] though, the reviews on quantum chemical modeling of 77 Se and 125 Te NMR spectra, have been published in a very scarce number by the moment. [33][34][35][36] The present review was conceived to fill this gap, focusing on the practical aspects of QC calculations of 77 Se and 125 Te NMR chemical shifts (CSs) and shielding constants (SCs) and the spin-spin coupling constants (SSCCs) involving these nuclei.…”

“…In particular, it is well known that SSCCs involving these nuclei are highly sensitive to structural changes, featuring a marked stereochemical behavior originating from their dependence on spatial orientation of selenium and tellurium lone pairs. [33,35] The calculated values can be applied then in establishing chemical structures, using only ordinary one-dimensional 77 Se and 125 Te NMR spectra, remaining the most common source of structural information nowadays.…”