Stand up for Electrostatics: The Disiloxane Case

Abstract

The basicity of the simplest silicone, disiloxane (H 3 SiÀ OÀ SiH 3 ), is strongly affected by the SiÀ OÀ Si angle (α). We use high-level ab initio MP2/aug'-cc-pVTZ calculations and the molecular electrostatic potential (MEP) to analyze the relationship between the increase in basicity and the reduction of α. Our results clearly point out that this increase can be explained through the MEP, as the interactions between oxygen from disiloxane and the acceptors are mostly electrostatic. Furthermore, the effect of α on the tetrel bond between disiloxane and several Lewis bases can again be rationalized using the MEP. Finally, we explore the cooperativity throughout α for ternary complexes where disiloxane simultaneously interacts with a Lewis acid and a Lewis base. Both non-covalent interactions remain cooperative for all α values, although the largest cooperativity effects are not always those maximizing the binding energy in the binary complexes. Overall, the MEP remains a powerful predictor for noncovalent interactions.

Hybrid Ligand Polymerization for Weakly Confined Lead Halide Perovskite Quantum Dots

“…Further experiments as shown in Figure S9 indicate an optional role of thiol-ene reaction, while the silyl ligand is essential to HLP. As the edge-shared tetrahedra are a strained surface defect with vibrations at 908 and 888 cm –1 , the reaction is strain activated , and the selectivity arises from the organic/inorganic resonance at 908 cm –1 , which is also corroborated by the accompanying vibration at 888 cm –1 in Figure S9. In addition, evidence for the multiple siloxane bond (Si–O–Si network), hydrophobic in nature, is confirmed by the much stronger vibration at around 800 cm –1 than the peak at 1261 cm –1 .…”

Transition from covalent to noncovalent bonding between tetrel atoms

“…Particularly when dealing with noncovalent interactions, it has been found useful to consider how the molecular electrostatic potentials (MEPs) of the two constituent monomers might best align with one another. [26][27][28][29][30][31][32][33] The MEPs of the three charge states of SnCl 2 are illustrated in Fig. 7.…”

Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

“…One, because of its tractable size we can also compare to C2OH6 using the same methodology. Two, there are very few previous studies, [5,6] which allows for a stringent proving ground. And three, there are previous works on its smaller counterpart SiOH4 [7][8][9][10][11][12][13][14], which allows for methodological testing.…”