Recent advances in computational liquid-phase ⁷⁷Se NMR

Abstract

This review aims to highlight significant progress in the calculation of 77Se NMR chemical shifts and spin – spin coupling constants involving selenium substantiated with a vast amount of experimental data. The material is arranged in two basic sections: the first one dealing with the calculation of 77Se NMR chemical shifts and the second one dealing with the computation of spin – spin coupling constants involving 77Se nucleus, namely 77Se–1H, 77Se–13C and 77Se–77Se together with some more exotic types of couplings, 77Se – 15N, 77Se–19F, 77Se–29Si and 77Se–31P. A special attention is focused on the stereoelectronic effects involving selenium atom and their manifestation in the 77Se NMR spectra of organoselenium compounds studied with the aid of the modern calculation of 77Se NMR parametres in combination with experimental results. The bibliography includes 114 references.

Acid‐Base and Anion Binding Properties of Tetrafluorinated 1,3‐Benzodiazole, 1,2,3‐Benzotriazole and 2,1,3‐Benzoselenadiazole

“…Previously, for relevant 1 : 1 complex between F À and 3,4-dicyano-1,2,5-telluradiazole obtained with TASF, 1 J( 125 TeÀ 19 F/ 19 FÀ 125 Te) = 1446 Hz was observed in 125 Te and 19 F NMR spectra. [4c] Normally, the ratio J( 125 TeÀ X)/J( 77 SeÀ X) is 2-3 (in absolute value, the signs are opposite), [23] and 1 J-( 77 SeÀ 19 F/ 19 FÀ 77 Se) of ~480 Hz, at least, can be expected for [10À F] À . In cocrystallizations of 10 with Ph 4 P + Cl À in molar ratios varied from 1 : 1 to 1 : 4, only starting materials were recovered by single-crystal XRD.…”

The aug‐cc‐pVTZ‐J basis set for the p‐block fourth‐row elements Ga, Ge, As, Se, and Br

“…We refrain here from comparing with the experimental results as one should recall that in our calculations, we have neither included vibrational corrections [76,77] nor treated any solvent effects, [78,79] as this is beyond the scope of this work. And most importantly, we will not be able to include relativistic effects, [64,80,81] as these so far are only implemented for DFT methods despite the recent publication of a relativistic SOPPA formalism. [64] Overall, there is no common conclusion for all molecules concerning the performance of the different methods.…”

Computational1H and13C NMR in structural and stereochemical studies

“…F I G U R E 3 CBS-estimated RMS deviations of (a) carbon and (b) proton isotropic shieldings from the empirical values in methane as a function of the method number (given in the abscissa axis): VXSC (1), HCTH (2), HCTH97 (3), HCTH147 (4), THCTH (5), M06L (6), B97D (7), B3LYP (8), B3P86 (9), B3PW91 (10), B1B95 (11), MPW1PW91 (12), MPW1LYP (13), MPW1PBE (14), MPW3PBE (15), B98 (16), B971 (17), B972 (18), PBE1PBE (19), B1LYP (20), O3LYP (21), BhandH (22), BHandHLYP (23), BMK (24), M06 (25), M06HF (26), M062X (27), tHCTHhyb (28), HSEh1PBE (29), HSE2PBE (30), PBEh1PBE (31), wB97XD (32), wB97 (33), wB97X (34), TPSSh (35), X3LYP (36), LC-wPBE (37), CAM-B3LYP (38), WP04 (39), RHF (40), MP2 (41), KT1 (42), KT2 (43), KT3 (44), SOPPA (45), SOPPA (CCSD) (46), and CCSD(T) (47). Reproduced from Kupka, et al [88] with the permission of the American Chemical Society Much later, Kupka, et al [88] performed a systematic study of the performance of about four dozens of different DFT functionals together with five pure nonempirical methods, RHF, MP2, SOPPA, SOPPA (CCSD), and CCSD(T), for predicting 1 H and 13 C NMR chemical shifts of six small molecules, NH 3 , CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , and C 6 H 6 , with using Jensen's pcS-n (n = 1-4) basis set.…”

“…Computation of NMR parameters provides a new guide in our understanding of the fundamental factors controlling stereochemistry and chemical reactivity of inorganic compounds, coordination complexes, organic and bioorganic molecules, [14][15][16][17][18][19][20][21][22][23][24][25][26] involving in particular natural products, [27][28][29][30][31][32][33][34] carbohydrates, [35][36][37][38] and carbonium ions. [39,40] Very recent results in this field appeared mainly in 2021 are outlined in the generalizing review by Kupka.…”