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Related Concept Videos

¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
Bond Energies and Bond Lengths02:49

Bond Energies and Bond Lengths

Stable molecules exist because covalent bonds hold the atoms together. The strength of a covalent bond is measured by the energy required to break it, that is, the energy necessary to separate the bonded atoms. Separating any pair of bonded atoms requires energy — the stronger a bond, the greater the energy required to break it.
Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must have a...
¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.

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Exploring Protein-Glycan Interactions: Advances in Nuclear Magnetic Resonance
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Correlating Pt-P bond lengths and Pt-P coupling constants.

Paul G Waddell1, Alexandra M Z Slawin, J Derek Woollins

  • 1School of Chemistry, University of St Andrews, St Andrews, ScotlandKY16 9ST.

Dalton Transactions (Cambridge, England : 2003)
|August 18, 2010
PubMed
Summary

This study reports the X-ray structures of platinum(II) complexes with varying phosphine ligands. A linear relationship was found between platinum-phosphorus bond length and the J{Pt-P} coupling constant for these platinum compounds.

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Area of Science:

  • Inorganic Chemistry
  • Crystallography
  • Organometallic Chemistry

Background:

  • Platinum complexes are crucial in catalysis and medicine.
  • Understanding the structural and electronic properties of platinum complexes is key to designing new materials.
  • Previous studies have investigated platinum halides with phosphine ligands.

Purpose of the Study:

  • To determine the X-ray crystal structures of a series of cis-dihaloplatinum(II) complexes containing various phosphine ligands.
  • To investigate the relationship between the Pt-P bond length and the J{Pt-P} coupling constant in these complexes.
  • To compare the structural data with previously reported chloride analogues.

Main Methods:

  • X-ray crystallography was employed to determine the three-dimensional structures of the synthesized platinum complexes.
  • The complexes studied include cis-PtBr(2)(P(OMe)(3))(2), cis-PtBr(2)(P(OMe)(2)Ph)(2), cis-PtBr(2)(P(OMe)Ph(2))(2), cis-PtBr(2)(PPh(3))(2), cis-PtI(2)(P(OMe)(3))(2), cis-PtI(2)(P(OMe)(2)Ph)(2), cis-PtI(2)(P(OMe)Ph(2))(2), and cis-PtI(2)(PPh(3))(2).
  • The obtained structural parameters were analyzed and compared with existing data for related compounds.

Main Results:

  • The X-ray structures of eight cis-dihaloplatinum(II) complexes with different phosphine ligands (varying methoxy and phenyl substituents) were successfully determined.
  • A linear correlation was established between the platinum-phosphorus bond length (l(Pt-P)) and the magnitude of the J{Pt-P} coupling constant.
  • The derived equation describing this relationship is l(Pt-P) = 2.421 -J/24255, applicable to the twelve complexes studied (including previously reported chloride analogues).

Conclusions:

  • The study confirms a predictable relationship between structural parameters (Pt-P bond length) and spectroscopic parameters (J{Pt-P} coupling) in platinum(II) phosphine complexes.
  • This finding provides a valuable tool for predicting structural features from spectroscopic data and vice versa.
  • The results contribute to a deeper understanding of structure-property relationships in organometallic platinum compounds.