Molecular geometry

Bridging qualitative modeling and accurate computations. A comparative study of simple nitrogen and phosphorus derivatives

Jack B. Levy, I. Hargittai

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The molecular geometries of a series of simple nitrogen and phosphorus derivatives have been computed in order to probe the validity of simple qualitative models of structural variations using a consistent set of data. The derivatives included NX3, ONX3, PX3, and OPX3 (X = F, CH3, CF3, SiH3). The computed geometries are consistent with experimental structures, where they are available, especially when parameter differences are considered. Further scrutiny of the bond-angle differences suggests that the MP2/6-31G* and MP3/6-31G* levels of theory are preferable for the nitrogen and phosphorus derivatives, respectively. Our observations include nitrogen bond lengthening and a slight closing of the XNX bond angles upon oxidation of nitrogen derivatives and phosphorus bond shortening and considerable opening of the XPX angles upon oxidation of phosphorus derivatives. These trends as well as the variations observed in nitrogen versus phosphorus comparisons are in agreement with the so-called "octet rule" and VSEPR predictions. As expected, the latter lose validity with increasing ligand versus central atom size and are replaced by the predominance of ligand-ligand non-bonded interactions.

Original languageEnglish
Pages (from-to)127-134
Number of pages8
JournalJournal of Molecular Structure: THEOCHEM
Volume454
Issue number2-3
Publication statusPublished - Nov 28 1998

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Phosphorus
phosphorus
Nitrogen
Derivatives
nitrogen
Geometry
geometry
Ligands
ligands
Oxidation
oxidation
Structural Models
octets
closing
trends
Atoms
probes
predictions
atoms
interactions

Keywords

  • Computed structures
  • Experimental structures
  • Molecular geometry
  • Nitrogen derivatives
  • Phosphorus derivatives

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "The molecular geometries of a series of simple nitrogen and phosphorus derivatives have been computed in order to probe the validity of simple qualitative models of structural variations using a consistent set of data. The derivatives included NX3, ONX3, PX3, and OPX3 (X = F, CH3, CF3, SiH3). The computed geometries are consistent with experimental structures, where they are available, especially when parameter differences are considered. Further scrutiny of the bond-angle differences suggests that the MP2/6-31G* and MP3/6-31G* levels of theory are preferable for the nitrogen and phosphorus derivatives, respectively. Our observations include nitrogen bond lengthening and a slight closing of the XNX bond angles upon oxidation of nitrogen derivatives and phosphorus bond shortening and considerable opening of the XPX angles upon oxidation of phosphorus derivatives. These trends as well as the variations observed in nitrogen versus phosphorus comparisons are in agreement with the so-called {"}octet rule{"} and VSEPR predictions. As expected, the latter lose validity with increasing ligand versus central atom size and are replaced by the predominance of ligand-ligand non-bonded interactions.",
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N2 - The molecular geometries of a series of simple nitrogen and phosphorus derivatives have been computed in order to probe the validity of simple qualitative models of structural variations using a consistent set of data. The derivatives included NX3, ONX3, PX3, and OPX3 (X = F, CH3, CF3, SiH3). The computed geometries are consistent with experimental structures, where they are available, especially when parameter differences are considered. Further scrutiny of the bond-angle differences suggests that the MP2/6-31G* and MP3/6-31G* levels of theory are preferable for the nitrogen and phosphorus derivatives, respectively. Our observations include nitrogen bond lengthening and a slight closing of the XNX bond angles upon oxidation of nitrogen derivatives and phosphorus bond shortening and considerable opening of the XPX angles upon oxidation of phosphorus derivatives. These trends as well as the variations observed in nitrogen versus phosphorus comparisons are in agreement with the so-called "octet rule" and VSEPR predictions. As expected, the latter lose validity with increasing ligand versus central atom size and are replaced by the predominance of ligand-ligand non-bonded interactions.

AB - The molecular geometries of a series of simple nitrogen and phosphorus derivatives have been computed in order to probe the validity of simple qualitative models of structural variations using a consistent set of data. The derivatives included NX3, ONX3, PX3, and OPX3 (X = F, CH3, CF3, SiH3). The computed geometries are consistent with experimental structures, where they are available, especially when parameter differences are considered. Further scrutiny of the bond-angle differences suggests that the MP2/6-31G* and MP3/6-31G* levels of theory are preferable for the nitrogen and phosphorus derivatives, respectively. Our observations include nitrogen bond lengthening and a slight closing of the XNX bond angles upon oxidation of nitrogen derivatives and phosphorus bond shortening and considerable opening of the XPX angles upon oxidation of phosphorus derivatives. These trends as well as the variations observed in nitrogen versus phosphorus comparisons are in agreement with the so-called "octet rule" and VSEPR predictions. As expected, the latter lose validity with increasing ligand versus central atom size and are replaced by the predominance of ligand-ligand non-bonded interactions.

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