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Formation of the elusive tetrahedral P₃N molecule.

ABSTRACT: The tetrahedral 1,2,3-triphospha-4-azatricyclo [1.1.0.0^2,4] butane (P₃N) molecule-an isovalent species of phosphorus (P₄)-was prepared in low-temperature (5 K) phosphine-nitrogen ices and was identified in the gas phase through isomer-selective, tunable, soft photoionization reflectron time-of-flight mass spectrometry. Theoretical calculations reveal that the substitution of a single phosphorus atom by nitrogen in the P₄ molecule results in enhanced spherical aromaticity while simultaneously increasing the strain energy from 74 to 195 kJ mol^-1. In P₃N, the P─P bond is shortened compared to those in P₄ by 3.6 pm, while the P─N─P bond angle of 73.0° is larger by 13.0° compared to the P─P─P bond angle of 60.0° in P₄. The identification of tetrahedral P₃N enhances our fundamental understanding of the chemical bonding, electronic structure, and stability of binary, interpnictide tetrahedral molecules and reveals a universal route to prepare ring strained cage molecules in extreme environments.

SUBMITTER: Zhang C

PROVIDER: S-EPMC9159698 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Formation of the elusive tetrahedral P3N molecule.

Zhang Chaojiang C Zhu Cheng C Eckhardt André K AK Kaiser Ralf I RI

Science advances 20220601 22

The tetrahedral 1,2,3-triphospha-4-azatricyclo [1.1.0.02,4] butane (P3N) molecule-an isovalent species of phosphorus (P4)-was prepared in low-temperature (5 K) phosphine-nitrogen ices and was identified in the gas phase through isomer-selective, tunable, soft photoionization reflectron time-of-flight mass spectrometry. Theoretical calculations reveal that the substitution of a single phosphorus atom by nitrogen in the P4 molecule results in enhanced sp ...[more]

PMID: 35648866

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