Investigation of Unusual N-(Triphenyl-λ5-phosphanylidene) Amide Fragmentation Observed upon MS/MS Collision-Induced Dissociation

A mechanism of unusual tandem (MS/MS) fragmentation of protonated species of N-(triphenyl-lambda(5)- phosphanylidene) derivatives, [M + H]+ to generate triphenylphosphine oxide (TPPO) within the mass spectrometer has been investigated and reported. Collision-induced dissociation of these molecules resulted in the generation of TPPO as a signature fragment. This fragment suggested the presence of a P-O bond in the structure which was contrary to the structure of the compound identified by nuclear magnetic resonance spectrometry (NMR) and single-crystal X-ray diffractometry (SXRD) techniques with a P=N bond rather than a P-O bond. In order to confirm the generation of the TPPO fragment within the mass spectrometer, 14 different N-(triphenyl-lambda(5)-phosphanylidene) derivatives containing amide, O-18-labeled amide, thiamide, and nonacyl phosphazene derivatives were synthesized and their MS/MS behavior was studied by liquid chromatography-high-resolution mass spectrometry. Fragmentation of these amide derivatives generated TPPO/TPPS or their O-18-labeled analogues as the major fragment in almost all cases under similar MS conditions. Based on the outcome of these experiments, a plausible mechanism for such fragmentation, involving the intramolecular shifting of oxygen from carbon to phosphorus, has been proposed. DFT calculations for the protonated species at B3LYP-D3/6-31+G(d,p) further supported the proposed mechanism involving a four membered ring, P-O-C-N, as the transition state. Details of this work are presented here.

Automated summary

This study investigates and reports an unusual tandem (MS/MS) fragmentation mechanism of protonated N-(triphenyl-lambda(5)-phosphanylidene) derivatives within the mass spectrometer, which generates the signature fragment triphenylphosphine oxide (TPPO). The presence of a P-O bond in the TPPO fragment contradicts the structure identified by nuclear magnetic resonance spectrometry (NMR) and single-crystal X-ray diffractometry (SXRD), which indicated a P=N bond. Synthesis and liquid chromatography-high-resolution mass spectrometry of 14 different N-(triphenyl-lambda(5)-phosphanylidene) derivatives confirmed the generation of TPPO/TPPS fragments, supporting a proposed mechanism involving intramolecular shifting of oxygen from carbon to phosphorus. The details of this work are presented in this article.