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Related Concept Videos

Valence Bond Theory02:42

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...
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Structural Isomerism02:34

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Metallic Solids02:37

Metallic Solids

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Coordination Number and Geometry02:57

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

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Related Experiment Video

Updated: May 28, 2026

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Published on: March 20, 2014

Allylpalladium dimers with metals connected by binucleating dithiooxamidates in two different coordination modes:

Santo Lanza1, Francesco Nicolò, Hadi Amiri Rudbari

  • 1Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone, 31 Contrada Papardo, 98166 Messina, Italy. lanza@unime.it

Inorganic Chemistry
|October 20, 2011
PubMed
Summary

New allylpalladium dimers were synthesized. Kinetic and thermodynamic isomers were identified, with chiral alkyl groups enabling endo/exo isomer detection in solution, and computational studies confirmed thermodynamic stability.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Allylpalladium complexes are versatile synthetic intermediates.
  • Dialkyldithiooxamidate ligands offer unique coordination possibilities.
  • Understanding ligand behavior in bimetallic systems is crucial for catalyst design.

Purpose of the Study:

  • To synthesize and characterize novel allylpalladium dimers bridged by dialkyldithiooxamidate ligands.
  • To investigate the formation of kinetic and thermodynamic isomers.
  • To explore the influence of alkyl substituents on isomer stability and detection.

Main Methods:

  • Synthesis of monochelate and bimetallic allylpalladium complexes.
  • Spectroscopic and diffractometric characterization techniques.
  • Computational studies to evaluate thermodynamic stability.

Main Results:

  • Successful preparation of allylpalladium dimers with various dialkyldithiooxamidate ligands.
  • Identification of distinct kinetic (κ-N,N'/κ-S,S') and thermodynamic (κ-N,S/κ-N',S') isomers.
  • Chiral alkyl groups were essential for observing endo/exo isomers in solution.
  • Kinetic isomers isomerize to more stable thermodynamic forms over time.

Conclusions:

  • Dialkyldithiooxamidate ligands can bridge two palladium centers in different coordination modes.
  • Ligand hemilability and alkyl substituent chirality influence isomer formation and stability.
  • Thermodynamic isomers are generally more stable, as supported by computational analysis.