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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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Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
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Structure and Nomenclature of Thiols and Sulfides02:17

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Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry,...
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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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Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Structural Preferences in Phosphanylthiolato Platinum(II) Complexes.

Josep Duran1, Alfonso Polo1, Julio Real2

  • 1Departament de Química Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.

Chemistryopen
|June 17, 2016
PubMed
Summary

This study explores platinum complexes with phosphanylthiolato ligands, detailing the synthesis and structure of a bis-chelate complex and a unique trinuclear complex. DFT calculations explain the observed stereochemistry and structural preferences.

Keywords:
P,S ligandsbis-chelate complexesdensity functional calculationsplatinumtrinuclear complexes

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Heterotopic phosphanylthiolato ligands are crucial in transition-metal chemistry.
  • The stereochemistry of metal complexes influences their reactivity.
  • Understanding ligand behavior in platinum complex formation is key.

Purpose of the Study:

  • To synthesize and characterize novel platinum complexes using phosphanylthiolato ligands.
  • To investigate the structural preferences and stereochemistry of these complexes.
  • To elucidate the factors governing the formation of mononuclear versus polynuclear platinum structures.

Main Methods:

  • Direct base-free substitution reactions with potassium tetrachloroplatinate(II).
  • Oxidative addition reactions with tetrakis(triphenylphosphine)platinum(0).
  • Single-crystal X-ray diffraction for structural determination.
  • Density Functional Theory (DFT) calculations for computational analysis.

Main Results:

  • Successful synthesis of the bis-chelate complex [Pt(SCH2CH2PPh2-κ(2) P,S)2] (1) with a cis-P,P arrangement, confirmed by DFT.
  • Formation of an unusual trinuclear complex [PtCl(μ-SCH2CH2PPh2-κ(2) P,S)]3 (2) instead of expected binuclear structures.
  • Structural characterization of complex 2 as a sulfur-bridging, edge-sharing cyclic trinuclear complex with a Pt3S3 skew-boat conformation.

Conclusions:

  • The cis-P,P arrangement in complex 1 is favored and rationalized by DFT.
  • Platinum exhibits a preference for forming trinuclear structures with these ligands under specific conditions.
  • Mechanistic and DFT studies provide insights into the formation of the observed trinuclear platinum complex.