On Transannulation in Azaphosphatranes: Synthesis and Theoretical Analysis

Abstract

A combined synthetic-theoretical study has been undertaken to determine the factors that influence transannulation in azaphosphatranes. The commonly used proazaphosphatrane P­(i-BuNCH2CH2)3N and several of its oxidized congeners are used as model systems. The haloazaphosphatranes of P­(i-BuNCH2CH2)3N were synthesized, including a rare fluoroazaphopshatrane, and used as references for computational investigations. Comparisons of the experimental and theoretical observations highlight the flexibility observed in transannulated atranes and the potential for multiple local energetic minima depending on the identity of the equatorial substituents for a given azaphosphatrane. Theoretical calculations also identify the role of the ethylene linker in azaphosphatrane bonding, the influence of transannulation on P–electrophile interactions, and the contribution of electrostatic interactions to transannulation.

Rhodium(i) complexes derived from tris(isopropyl)-azaphosphatrane—controlling the metal–ligand interplay

“…4, panel A), which falls into the same range but is slightly stronger than the corresponding interaction in chloro-and iodo-azaphosphatranes (7.10 and 5.16 kcal mol À1 , respectively). 21 The bonding character is also veried by the atoms-in-molecules (AIM) method, revealing a bond critical point BCP (3,À1) located between the P and the N ax atoms (Fig. 4, panel B).…”

Azaphosphatranes Catalyzed Strecker Reaction in the Presence of Water

“…More recently, azaphosphatranes have been shown to act as subcomponents in the construction of tetrahedron cages for anion encapsulation and extraction [11] . In addition, Johnson and co‐workers studied the factors that affect transannulation in azaphosphatranes, which further shed light on this bicyclic architecture [12] . These recent insights highlight the growing interest aroused by azaphosphatranes, to lead to new and original applications.…”

Twenty years of exceptional success: The molecular education and research consortium in undergraduate computational chemistry (MERCURY)

“…The faculty published 2 peer‐reviewed books, [ 238,239 ] 9 peer‐reviewed book chapters, [ 240–248 ] and 115 peer‐reviewed research papers. [ 249–363 ] This comes to 1.6 peer‐reviewed products/faculty/year during the 3‐year grant period, which is 3.2 times the rate of publication for natural science faculty at PUIs. [ 46 ]…”

“…Kelling Donald's research: In the Donald research group, work is focused on (a) halogen bonding and other sigma hole interactions in organic and inorganic systems, [ 210,278 ] (b) fluxionality in planar inorganic clusters and the nature and potential control of so‐called molecular machines, [ 208,263 ] (c) the evolution of structural preferences and thermal stability in metal halide and hydride molecules, clusters, and corresponding extended solids, [ 322 ] (d) the stability and catalytic applications of structurally interesting or unusual main‐group and transition‐metal organometallic compounds, [ 151,231,351,385 ] (e) the stabilization of unusual bonding arrangements, including planar tetra‐coordinate and other unusual coordination environments, [ 172 ] (f) quantifying currently qualitative but transferrable concepts in chemical bonding, [ 233 ] and (g) aromaticity and analogous phenomena in non‐hydrocarbon systems. [ 338,386 ] The MRI resources are essential for calculations on large and heavy elemental systems.…”