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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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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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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

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Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
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Electrophilic Addition to Alkynes: Halogenation02:38

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Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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Valence Bond Theory

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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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Carbocations02:10

Carbocations

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Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Alkyl Bismuth Cations: Synthesis, Characterization, and Application as Z-Type Ligands.

Johannes Schwarzmann1,2, Joel Nitzsche1,2, Cissie Slopianka1,2

  • 1Department of Inorganic Chemistry, Philipps Universität Marburg, Marburg, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|February 25, 2026
PubMed
Summary

Researchers synthesized novel alkyl bismuth cations with cyclic motifs and longer alkyl chains, expanding organobismuth chemistry. These cations function as soft Z-type ligands, forming unique metal-only Lewis pairs with platinum complexes.

Keywords:
Z‐type ligandsalkyl bismuth cationsbismanecyclopropylmetal‐only Lewis pairs

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Materials Science

Background:

  • The chemistry of alkyl bismuth cations is underdeveloped compared to aryl counterparts.
  • A knowledge gap exists in the synthesis and reactivity of alkyl bismuth compounds.

Purpose of the Study:

  • To develop synthetic protocols for novel alkyl bismuth precursors.
  • To synthesize and characterize the first alkyl bismuth cations with longer alkyl chains and cyclic motifs.
  • To investigate the ligand properties of these novel cations.

Main Methods:

  • Synthesis of bismacyclic and cyclopropyl bismuth precursors.
  • Conversion of precursors to cationic alkyl bismuth species [BiR2(SbF6)].
  • Reaction of cations with platinum(0) precursor [Pt(PCy3)2] to form metal-only Lewis pairs.

Main Results:

  • Successful synthesis of Bi(CH2)5Br, BicPr2Cl, and BiiPr2Cl precursors.
  • Formation of cationic species [BiR2(SbF6)] with R2 = (CH2)5, cPr2, iPr2.
  • Isolation and characterization of platinum-bismuth complexes with unsupported Pt→Bi bonds.
  • Identification of Pt oxidation and cyclopropyl ring-opening as decomposition pathways.

Conclusions:

  • Established new synthetic routes for alkyl bismuth cations.
  • Demonstrated the utility of these cations as soft Z-type ligands.
  • Reported the first metal-only Lewis pairs involving alkyl bismuth cations and platinum.