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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.
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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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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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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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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Color in Coordination Complexes
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Polysulfido Chain in Binuclear Zinc(II) Complexes.

Kamal Hossain1, Amit Majumdar1

  • 1School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A and 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.

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This study details the synthesis and reactivity of novel binuclear zinc complexes, including a unique pentasulfido complex. These complexes demonstrate versatile sulfur chain chemistry and potential for generating organosulfur compounds.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Sulfur Chemistry

Background:

  • Binuclear zinc complexes offer unique reactivity platforms.
  • Understanding sulfur chain coordination is crucial for catalysis and materials science.
  • The BPMP ligand provides a stable scaffold for binuclear metal centers.

Purpose of the Study:

  • To synthesize and characterize a binuclear zinc(II) bis(benzenethiolate) complex.
  • To investigate the reactivity of this complex, leading to an unprecedented binuclear zinc(II) pentasulfido complex.
  • To explore the chemical transformations and synthetic utility of the pentasulfido complex.

Main Methods:

  • Synthesis of binuclear zinc(II) complexes: [Zn2(BPMP)(SPh)2]+ and [Zn2(BPMP)(μ2-S5)]+.
  • Oxidation reactions using Cp2Fe+ and elemental sulfur (S8).
  • Reactions with phosphines (PPh3, Ph2PCH2CH2PPh2), acids (HBF4), and organic compounds (PhCOOH, MeCOSH, PhCH2Br, PhC(O)Cl).

Main Results:

  • Successful synthesis of [Zn2(BPMP)(SPh)2]+ and the novel [Zn2(BPMP)(μ2-S5)]+ complex.
  • Demonstrated reactivity of the pentasulfido complex with PPh3 to yield Ph3PS and a hydroxo complex, and with Ph2PCH2CH2PPh2 to form a tetrathio complex.
  • Showcased proteolysis of the S5 chain with acids and organic electrophiles, generating various zinc complexes and organosulfur compounds.

Conclusions:

  • The binuclear zinc pentasulfido complex exhibits rich reactivity, enabling controlled sulfur chain transformations.
  • This chemistry provides a pathway for synthesizing diverse organosulfur compounds.
  • The study highlights the potential of binuclear zinc complexes in sulfur chemistry and synthetic applications.