Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism

Published

December 22, 2008

Author(s)

Yi-Lei Zhao, Jason W. Flora, Stephen Garrison, Carlos A. Gonzalez, K. N. Houk, Manuel Marquez

Abstract

A yellow solid material [PxHy] has been obtained in the reaction of phosphine (PH3) and nitric oxide (NO) at room temperature, and characterized by TGA-MS and ATR-FTIR, along with the previous SEM and X-ray fluorescence spectroscopy. In this work using Complete Basis Set (CBS-QB3) methods, a plausible mechanism has been investigated for the phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab. initio method suggest: a) instead of the monomer, the nitric oxide dimer acts as an initial oxidant, b) the resulting phosphine oxides (H3P=O ↔ H3P+O−) in the gas phase draw each other via strong dipolar interactions between the P-O groups, c) consequently an auto-catalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations, a series of cluster models were computed to simulate the polymerization.

Citation

Macromolecules

Volume

48

Issue

3

Pub Type

Journals

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Keywords

phosphine, nitric oxide, polyhydride phosphorus polymer

Citation

Zhao, Y. , Flora, J. , Garrison, S. , Gonzalez, C. , Houk, K. and Marquez, M. (2008), Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism, Macromolecules, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=832368 (Accessed October 5, 2024)