A theoretical investigation into novel germylenes: effects of nitrogen substitution on stability and multiplicity

Estimating the stability and reactivity of novel bicyclic germylenes at density functional theory

“…[28,29] Full geometry optimizations are performed by the B3LYP [30][31][32] and the standardized 6-311+ +G** basis set. [19,33,34] Also, the natural bond orbital (NBO) population analysis on optimized divalents is calculated at B3LYP/6-311++G**. [19] Structural parameters including bond distances, bond angles, and symmetries are also calculated at the same level of theory.…”

“…[19,33,34] Also, the natural bond orbital (NBO) population analysis on optimized divalents is calculated at B3LYP/6-311++G**. [19] Structural parameters including bond distances, bond angles, and symmetries are also calculated at the same level of theory. In density functional theory calculations, Becke's three-parameter exchange functional (B3) mixed with gradient-corrected correlation functional of Lee, Yang, and Parr (LYP) (example of the generalized gradient approximation [GGA] function).…”

“…[18] In contrast to carbenes, germylenes have mainly singlet ground states. [19][20][21] In fact, the lone pair electrons on -G̈e-increase s atomic orbital character with increasing atomic size. Therefore, the preparations of triplet ground states of germylenes are one of the most challenging issues in the modern organometallic chemistry of germanium.…”

“…[23][24][25][26][27] In 1987, Veith succeeded to synthesize the first NHGes with a four-membered structure stabilized by two nearby nitrogens. [19,27] In our continued quest for novel divalent NHgermylene species, [19] the question immediately arises whether stable bicyclic germylenes with one, two, and three germylene centers are researchable and how nitrogen substitutions may influence their stability, multiplicity (singlet [s] vs. triplet [t]), band gap (ΔE HOMO-LUMO ), nucleophilicity (N), electrophilicity (ω), isodesmic reaction, and geometrical parameters at B3LYP/6-311++G** level of theory (Tables 1-9).…”

DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

“…In order to obtain the precise energy corresponding to the experimental reaction solvent system, we used a larger basis set to recalculate the single-point energy of all optimized geometries in the corresponding experimental solvents. This is also a widely used method to obtain accurate energy in catalytic reactions [30][31][32][33][34]. The larger basis set of 6-311 + + G (d, p) (SDD with ECP for Au) in the SMD implicit solvent environment [35] with acetonitrile (solvent = CH 3 CN, ε = 35.688) is used.…”