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¹H NMR: Long-Range Coupling

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.

2D NMR: Overview of Heteronuclear Correlation Techniques

2D NMR: Overview of Heteronuclear Correlation Techniques

Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an X-nucleus, such as carbon-13 or nitrogen-15. This method is commonly used in nuclear magnetic resonance (NMR) spectroscopy to gain insights into complex chemical compounds' structural and compositional aspects. A typical heteronuclear correlation spectrum displays X-nucleus chemical shifts on one axis and a proton spectrum on the other axis.

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

Valence Bond Theory

Valence Bond Theory

Overview of Valence Bond Theory

Bonding in Metals

Bonding in Metals

Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”.

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...

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Related Experiment Video

Updated: Jun 24, 2026

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Published on: May 28, 2014

Long-range through-bond heteronuclear communication in platinum complexes.

Olena V Zenkina¹, Leonid E Konstantinovski, Linda J W Shimon

¹Department of Organic Chemistry, The Weizmann Institute of Science, 76100 Rehovot, Israel.

Inorganic Chemistry

|April 3, 2009

Summary

Platinum complexes show unexpected long-range nuclear spin-spin coupling through bonds, not space. This discovery in platinum (Pt), phosphorus (P), and fluorine (F) nuclei communication over 1.3 nm distances opens new avenues in materials science.

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Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Published on: June 24, 2022

Area of Science:

Organometallic Chemistry
Nuclear Magnetic Resonance Spectroscopy
Solid-State Chemistry

Background:

Long-range heteronuclear spin-spin coupling is crucial for understanding molecular structure and electronic communication.
Platinum complexes are vital in catalysis and materials science, but their spin-spin coupling properties are not fully explored.

Purpose of the Study:

To investigate unusual long-range heteronuclear spin-spin coupling in platinum stilbene- and stilbazole-based complexes.
To elucidate the mechanism and extent of nuclear communication through bonds versus through space.

Main Methods:

Synthesis and single crystal analysis of platinum complexes.
Solution-state Nuclear Magnetic Resonance (NMR) experiments, including (19)F{(1)H}, (31)P{(1)H}, and (195)Pt{(1)H} spectra.
gNMR simulations and Density Functional Theory (DFT) calculations.

Main Results:

Observed significant long-range spin-spin couplings between (195)Pt and (19)F nuclei over seven bonds ((7)J(PtF) = 2.9 Hz) and between (31)P and (19)F nuclei over eight bonds ((8)J(PF) = 11.8 Hz).
A notable six-bond coupling ((6)J(PtF) = 40.1 Hz) was found in a related pyridinium complex.
NMR spectral analysis revealed complex spin systems, indicating through-bond communication over distances of 0.9-1.3 nm.

Conclusions:

The study demonstrates through-bond communication in platinum complexes, challenging previous assumptions about spin-spin coupling mechanisms.
The observed long-range couplings are attributed to a pi-conjugated metal-ligand network.
These findings provide new insights into the electronic structure and properties of platinum-based materials.