An electron localization function investigation of bonding in some simple four‐coordinate nitrogen and phosphorus compounds

Chesnut, D. B.

doi:10.1002/1098-1071(2000)11:5<341::aid-hc5>3.0.co;2-#

Cited by 17 publications

(8 citation statements)

References 51 publications

(50 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5, the disynaptic valence basins are always located closer to the most electronegative atom. The ELF descriptions of HCN, H 2 C=NH, and H 2 C=PH obtained here agree with the same type of study performed by Chesnut [53].…”

Section: Elf Bonding Analysissupporting

confidence: 87%

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

et al. 2012

View full text Add to dashboard Cite

The nature of the C-As bonds present in a series of six neutral and anionic arsaalkynes was investigated. The optimized geometries, vibrational frequencies, and wavefunctions of all the studied species were computed using density functional theory (B3LYP/6-311??G(2d,2p)). To understand the bonding characteristics, Atoms in Molecules theory and topological analysis of the electron localization function were used. For comparison, natural bond orbital analysis was also performed. The results suggest that in five of the six studied compounds, the C-As bonds are essentially triple bonds, with similar characteristics to the C-P analogues in phosphaalkynes.

show abstract

Section: Elf Bonding Analysissupporting

confidence: 87%

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

et al. 2012

View full text Add to dashboard Cite

show abstract

“…The V(P−O), V(P−O H ), and V(O−H) domains are cylindrical and demonstrate the bonding interaction typical for single bonds. At η( r ) = 0.815 the bonding between P and O atoms in [Pt 2 (pop) 4 ] 4- resembles that calculated for the H 3 PO molecule, in which the P−O bond was described as having both polarized covalent and ionic character . At η( r ) = 0.815, a localization domain is visible between platinum and phosphorus, located close to the latter atom.…”

Section: Theoretical Results and Comparison With Experimentmentioning

confidence: 59%

Theoretical Analysis of the Triplet Excited State of the [Pt₂(H₂P₂O₅)₄]⁴^- Ion and Comparison with Time-Resolved X-ray and Spectroscopic Results

2003

View full text Add to dashboard Cite

A full understanding of the nature of excited states of transition metal complexes is important for understanding their chemical reactivity and role as intermediates in photochemically induced reactions. The ground and excited states of the [Pt(2)(pop)(4)](4-) ion are investigated using density functional theory (DFT). Calculations with different functionals employing quasi-relativistic Pauli and ZORA formalisms all predict a Pt-Pt bond shortening and a slight Pt-P lengthening upon excitation to the lowest triplet state, the latter in apparent contradiction to experimental EXAFS results. The PW86LYP functional with the ZORA relativistic treatment is found to produce good agreement with time-resolved crystallographic and spectroscopic results. A topological bond path between the Pt atoms is found in both the ground and the excited states, though the electron localization function (ELF) indicates weak Pt-Pt covalent bonding for the excited state only. The spin density is mainly localized on the Pt atoms, giving insight into the ability of the triplet excited state to abstract hydrogen and halogen atoms from organic substrates.

show abstract

“…Triphenylphosphane oxide (Ph 3 PO) is known to exist as a monomer with a tetrahedral geometry at the phosphorus center, and X-ray crystallographic analysis of Ph 3 PO 3 disclosed that the PO bond length (1.46 Å) is significantly shorter than the ideal value for the P−O single-bond length (1.65 Å) . Recent theoretical studies on a parent phosphane oxide (H 3 PO) have concluded that the contribution of the ionic canonical form P + −O - would be important for explaining this bond shortening …”

Section: Introductionmentioning

confidence: 99%

Diverse Structures and Remarkable Oxidizing Ability of Triarylbismuthane Oxides. Comparative Study on the Structure and Reactivity of a Series of Triarylpnictogen Oxides

et al. 2004

View full text Add to dashboard Cite

A systematic series of triarylbismuthane oxides was prepared in order to disclose their structure and reactivity, which have been compared with those of lighter pnictogen counterparts. X-ray crystallographic analysis of tris(2-methoxyphenyl)bismuthane oxide and tris(2-methoxyphenyl)stibane oxide revealed that they exist as dimers with a flat bis(µ-oxo) ring, implying that the polarized Bi + -Oand Sb + -Obonds aggregate to attain electrostatic stabilization. In sharp contrast to their phosphorus, arsenic, and antimony counterparts, triarylbismuthane oxides are thermally unstable and possess a high oxidizing ability. In particular, the bismuthane oxides bearing ortho-substituted aryl ligands oxidized primary and secondary alcohols to aldehydes and ketones, respectively, with high efficiency under mild conditions.

show abstract

An electron localization function investigation of bonding in some simple four‐coordinate nitrogen and phosphorus compounds

Cited by 17 publications

References 51 publications

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

Theoretical Analysis of the Triplet Excited State of the [Pt₂(H₂P₂O₅)₄]⁴^- Ion and Comparison with Time-Resolved X-ray and Spectroscopic Results

Diverse Structures and Remarkable Oxidizing Ability of Triarylbismuthane Oxides. Comparative Study on the Structure and Reactivity of a Series of Triarylpnictogen Oxides

Contact Info

Product

Resources

About

An electron localization function investigation of bonding in some simple four‐coordinate nitrogen and phosphorus compounds

Cited by 17 publications

References 51 publications

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

The nature of the C–As bonds in arsaalkynes: an atoms in molecules and electron localization function study

Theoretical Analysis of the Triplet Excited State of the [Pt2(H2P2O5)4]4- Ion and Comparison with Time-Resolved X-ray and Spectroscopic Results

Diverse Structures and Remarkable Oxidizing Ability of Triarylbismuthane Oxides. Comparative Study on the Structure and Reactivity of a Series of Triarylpnictogen Oxides

Contact Info

Product

Resources

About

Theoretical Analysis of the Triplet Excited State of the [Pt₂(H₂P₂O₅)₄]⁴^- Ion and Comparison with Time-Resolved X-ray and Spectroscopic Results