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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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...
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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...
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Complexation Equilibria: The Chelate Effect01:19

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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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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.
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Structural Isomerism02:34

Structural Isomerism

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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.
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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
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Phosphorus-Chalcogen Ring Expansion and Metal Coordination.

Cameron M E Graham1, Juuso Valjus2, Taylor E Pritchard1

  • 1Department of Chemistry and the Centre for Advanced Materials and Biomaterials Research, Western University , 1151 Richmond Street, London, Ontario N6A 5B7, Canada.

Inorganic Chemistry
|October 14, 2017
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Summary

Reactivity of four-membered phosphorus-chalcogen rings was explored. These rings expand to more stable six-membered rings upon Lewis base addition, forming tripodal metal complexes.

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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
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Area of Science:

  • Organophosphorus chemistry
  • Inorganic chemistry
  • Materials science

Background:

  • Four-membered rings containing phosphorus in the +3 oxidation state exhibit unique reactivity.
  • Understanding the stability and transformation of these heterocyclic compounds is crucial for developing new materials and catalysts.

Purpose of the Study:

  • To investigate the ring expansion reactions of four-membered (RPCh)2 rings (Ch = S, Se).
  • To elucidate the mechanism of formation for the resulting six-membered (RPCh)3 rings.
  • To explore the coordination chemistry of these rings with coinage metals.

Main Methods:

  • Experimental studies involving Lewis base addition to four-membered rings.
  • Density functional theory (DFT) calculations to investigate reaction mechanisms.
  • Reactions with coinage metals to form coordination complexes.

Main Results:

  • Four-membered (RPCh)2 rings readily undergo ring expansion to more stable six-membered (RPCh)3 rings in the presence of Lewis bases.
  • Two plausible reaction mechanisms involving phosphinidene chalcogenide intermediates were identified computationally.
  • Both four- and six-membered rings react with coinage metals to yield tripodal complexes where the (RPCh)3 ring coordinates through a phosphorus atom.

Conclusions:

  • The ring expansion of four-membered phosphorus-chalcogen rings to more stable six-membered systems is a facile process.
  • The reaction mechanism involves phosphinidene chalcogenide intermediates, offering insights into phosphorus-chalcogen bonding.
  • The resulting six-membered rings can act as versatile ligands for coinage metals, forming novel coordination compounds.