The complicating role of pnictogen bond formation in the solution-phase and solid-state structures of the heavier pnictogen atranes

Abstract

The structure of the simplest stibatrane has been a mystery since it was first prepared in 1966. This study reports the preparation and characterization of two stibatranes from triethanolamine and...

Influence of Internal Angular Arrangement on Pnicogen Bond Strength

“…There have been several such molecules synthesized and studied to date. The stibatrane molecule designed by Moaven et al 45 situates three internal five-membered rings into a cage as illustrated in Figure 5a. The prototypical example of a unit with no internal strain is Bi(OH) 3 in Figure 5b.…”

“…Even with the decline in the average bond energy with n, the highly pyramidal coordination of the ZO 3 CH units keeps this bond energy from sinking below 7 kcal/mol, even when there are three bonds present and when the Z atom is P. All told, the strongest bond of 20.3 kcal/mol is connected with the BiO 3 CH system. As a point of comparison with experiment, Moaven et al had recently measured 45 a ZB energy of 6 kcal/mol for Sb-atrane with an O electron donor. This value compares very well with the calculated value of 9.7 kcal/mol for the stronger N donor considered here.…”

“…Like the other related noncovalent bonds of this type, ZBs seldom contain a first-row atom, in this case N, as the Lewis acid atom, due in large measure to its high electronegativity, which resists σ-hole formation. Although the presence of one such ZB inhibits the formation of a second such bond to the same Z atom due to negative cooperativity, the tendency toward such bonding is sufficiently compelling that two, three, and even more such bonds have been observed. − …”

Extending Chirality in Group XIV Metallatranes

“…Rather prominent among these is the use of tricarbametallatranes as reagents in organic syntheses , and of inorganic metallatranes lacking any metal–carbon bond as catalysts for polylactide and polyurethane formation. , Furthermore, metallatranes were also used in materials science . Last but not least, the cage-type metallatrane compounds were used as models for academic studies such as nucleophilic substitution at hypercoordinated group XIV element centers , and nontraditional differential mobility behavior…”

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

“…It has been observed in a varied set of crystals [ 11 , 12 , 13 , 14 , 15 , 16 ], and in the gas phase [ 17 ]. Experimental observations have been made in matrices [ 18 , 19 , 20 , 21 ] and via NMR measurements [ 22 , 23 ], and there are some experimental estimates of PnB energies [ 24 ] available. PnBs are involved in numerous chemical functions such as the capture and transport of halides across a phospholipid membrane [ 25 ].…”