Chemistry of Intermolecular Frustrated Lewis Pairs in Motion: Emerging Perspectives and Prospects. Issue 2 (9th February 2015)

• Record Type: Journal Article
• Authors: Pu, Maoping; Privalov, Timofei
• Is Part Of: Israel journal of chemistry. Volume 55:Issue 2(2015)
• Page Start: 179
• Page End: 195
• Publication Date: 2015-02-09
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/ijch.201400159
• Languages: English
• ISSNs: 0021-2148

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>This feature article describes the chemistry in motion of frustrated Lewis pairs (FLPs). With state‐of‐the‐art <italic>ab initio</italic> molecular dynamics (AIMD) simulations supplemented by minimum energy path (MEP) and potential energy surface (PES) calculations, we examine the binding of CO<sub>2</sub> and the heterolytic cleavage of H<sub>2</sub> by a Lewis base (LB), <italic>t</italic>Bu<sub>3</sub>P, and a Lewis acid (LA), B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>. We strive to uncover and understand mechanistic implications of the physical laws that govern the behavior of a LB and a LA when they react with a third species (e.g., CO<sub>2</sub> or H<sub>2</sub>) at finite temperature. The approximation that we necessarily must make at present is to forgo the quantization of the movement of atoms in favor of the Born‐Oppenheimer molecular dynamics (BOMD), which unfold according to the classical (Newton's) laws of motion. However, strict quantum chemical theory is used to compute all of the forces that govern the dynamics of the macromolecular FLP system. Using physical reasoning and innovative computer simulations, we show that multi‐scale motion is the predominant mechanistic aspect in reactions of the <italic>t</italic>Bu<sub>3</sub>P/B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> FLP, as well as, conceivably, those of other similar intermolecular FLPs. Insight achieved thus far leads to a novel activity model for intermolecular FLPs and specific predictions, which could be useful for future experimental and theoretical studies of FLP and other chemistries.</p> </abstract>