# Metal‐Free Scission of the NO+ Triple Bond

## TL;DR

This paper describes a method to break one of the strongest chemical bonds, the NO+ triple bond, at room temperature without using metals.

## Contribution

A metal-free method for cleaving the NO+ triple bond at room temperature is presented.

## Key findings

- The NO+ triple bond was completely cleaved to form a new compound at room temperature.
- An intermediate with a novel P═N−O−P+ motif was isolated at −30°C.
- Quantum calculations and NMR studies revealed the reaction mechanism and kinetics.

## Abstract

We report the facile and direct room temperature unimolecular scission of the N≡O+ triple bond, one of the strongest known chemical bonds with a bond dissociation energy of 1049 kJ mol−1. The reaction of NO[Al(ORF)4] (RF = C(CF3)3) and PNP
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Bu (2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine) in CH2Cl2 yields the 1,2,3‐diazaphospholo[1,5‐a]pyridinium derivative [DAPP
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Bu]+[Al(ORF)4]– (1), featuring the complete cleavage of the N≡O+ bond. At −30°C, the reaction intermediate [PNOP
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Bu]+[Al(ORF)4]– (2), which contains the novel bridging P═N−O−P+ motif, can be isolated. Mechanistic insights were gained through quantum chemical calculations, which elucidated the formation pathways of 1 and 2, while NMR spectroscopic kinetic studies quantified the conversion rate from 2 to 1.

Breaking bonds: The reaction between NO[Al(ORF)4] (RF = C(CF3)3) and the diphosphane PNP
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Bu (2,6‐bis(di‐tert‐butylphosphino‐methyl)pyridine) leads to the direct and complete cleavage of the NO+ triple bond, one of the strongest chemical bonds known. The mechanism of this reaction was studied using quantum chemical calculations and NMR spectroscopic kinetics investigations.