Accessing an Aromatic Diphosphatriazolate Anion by Formal Inorganic “Click” Chemistry

Abstract

High five: A formal cycloaddition reaction between a chemical source of P2 and azide (N3)− affords the novel [P2N3]− ion. Experimental and computational investigations confirm the presence of substantial aromaticity within this exciting new building block in inorganic chemistry.

Search for aromatic anions in the P2E3− (E = N, P, As, Sb, Bi) series

“…Chem. Phys., 2016, 18, 16084--16087 | 16087 aromatic pnictogen-containing heterocycles 15,[25][26][27] allows us to expect that the present contribution will stimulate further development of this research field.…”

Negative ion photoelectron spectroscopy of P2N3−: electron affinity and electronic structures of P2N3˙

“…A recent report by Velian et al of the successful synthesis of large amounts of a salt containing diphosphatriazolate (P 2 N 3 – , see Scheme 1 ) anion marks a breakthrough in synthetic phosphorus–nitrogen chemistry. 27 , 28 As a 6π-electron aromatic species with a planar five-membered ring, P 2 N 3 – belongs to the set of (P n N 5– n ) – ( n = 0–5) anions, which, except for the n = 5 member of this series, have until now remained elusive. Considering the substantial enrichment of inorganic and organometallic chemistry made possible by the discovery of cyclo -P 5 – , one may anticipate that the synthesis of bottleable P 2 N 3 – will impact chemistry in a similar way.…”

A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN3–

“…Until recently, the cyclo -pentaphosphorus anion (P 5 – ) represented the only all-pnictogen analogue of cyclopentadienide anion (C 5 H 5 – ) − that could be synthesized and isolated in bulk quantities. − Although the cyclo -pentazolate anion (N 5 – ) was observed in the gas phase more than a decade ago and has been calculated to be a stable species, attempts to synthesize it in large quantities have, at least thus far, been futile . Consequently, the recent synthesis of P 2 N 3 – represents important progress in the study of all-pnictogen analogues of C 5 H 5 . − …”