Abstract
The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.
Highlights
(Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century
We have reexamined the geometric aspects of phosphoruscentered intra- and inter-molecular interactions in several crystal structures, selected for illustrative purposes, that have been deposited in the CSD and ICSD databases
They are smaller, and this could be successfully explained as attractive interactions that occur between interacting regions of positive and negative potential, elucidated using the molecular electrostatic surface potential (MESP) model
Summary
Noncovalent interactions are one of the chemical interactions (or chemical synthons) that have been explored for some time [1,2] and continue to be elucidated [3,4]. The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, can be identified when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. The characteristics and features used to define the three types of noncovalent interactions mentioned above may be transferable to elements of the pnictogen family In this overview, we make explicit use of the “sum of the van der Waals radii” concept [48] and directional features [49–51] to identify pnictogen bonding in the crystals examined. We stress that our aim is to bring to the reader’s attention examples of these systems, and we make no claim about the comprehensiveness of our survey
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