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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 most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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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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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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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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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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Complexes of monocationic Group 13 elements with pentaphospha- and pentaarsaferrocene.

Martin Fleischmann1, Stefan Welsch, Hannes Krauss

  • 1Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 12, 2014
PubMed
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New coordination polymers form from sandwich complexes and Group 13 metals. These materials show dynamic coordination behavior in solution, offering insights into metal-ligand interactions.

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NMR spectroscopyX-ray diffractionarsenicphosphorussandwich complexes

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Sandwich complexes featuring phosphorus (P) and arsenic (As) rings, specifically [Cp*Fe(η(5)-E5)] (Cp*=η(5)-C5Me5; E=P, As), are known precursors in coordination chemistry.
  • Group 13 metals (Tl, In, Ga) in their monovalent state, stabilized by weakly coordinating anions like [Al{OC(CF3)3}4](-), offer unique reactivity profiles.
  • Understanding the assembly and bonding in novel coordination polymers is crucial for developing new materials with tailored properties.

Purpose of the Study:

  • To investigate the reactions between sandwich complexes [Cp*Fe(η(5)-E5)] and monovalent Group 13 metal cations.
  • To synthesize and characterize novel one-dimensional coordination polymers and coordination compounds.
  • To explore the influence of weakly coordinating anions on the structural and dynamic properties of these complexes.

Main Methods:

  • Synthesis of novel coordination polymers and compounds.
  • Single-crystal X-ray diffraction for structural determination.
  • NMR spectroscopy (including 31P MAS NMR), ESI-MS, and osmometric molecular-weight determination to study solution behavior.
  • Density Functional Theory (DFT) calculations for mechanistic insights.

Main Results:

  • One-dimensional coordination polymers [M(μ,η(5):η(1)-E5FeCp*)3][TEF]n were successfully synthesized for E=P, As and M=Tl, In, Ga.
  • Structural analysis revealed η(5)-bound E5 ligands and weak σ-interactions between the E5 ring and Group 13 metal cations.
  • Exchanging the weakly coordinating anion ([TEF]- for [FAl]-) in a thallium complex resulted in a compound lacking σ-interactions.
  • Dynamic coordination behavior in solution was observed and supported by spectroscopic and analytical methods.
  • The crystal structure of the starting material [Cp*Fe(η(5)-As5)] was determined.

Conclusions:

  • The reactions lead to the formation of novel coordination polymers and compounds with tunable structural features based on the anion.
  • Weak σ-interactions play a role in the assembly of these complexes, and their presence can be modulated by anion choice.
  • The observed dynamic coordination behavior in solution highlights the fluxional nature of these organometallic systems.
  • DFT calculations provide valuable insights into the equilibrium of these dynamic processes.