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Transition metal thioether complex

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Transition metal thioether complexes comprise coordination complexes of thioether (R2S) ligands. The inventory is extensive.

Dimethylsulfide complexes

As the simplest thioether, dimethylsulfide forms complexes that are illustrative of the class.[1] Well characterized derivatives include cis-[TiCl4L2], VCl3L2, NbCl5L, NbCl4L2, Cr(CO)5L, CrCl3L3, RuCl2L4, RuCl3L3, RhCl3L3, cis- and trans-[IrCl4L3]-, cis-MCl2L2 (M = Pd, Pt), [PtCl3L]-, cis- and trans-[PtCl4L2] (L = SMe2). With respect to donor properties, dimethylsulfide is a soft ligand with donor properties weaker than phosphine ligands.[2]

Stereochemistry

Structure of [Ru(NH3)5(SMeEt)]2+.[3]

Thioether complexes feature pyramidal sulfur centers. Typical C-S-C angles are near 99° in both free thioethers and their complexes. The C-S distance in dimethylsulfide is 1.81 Å, which is also unaffected in its complexes.[4]

Diastereotopic methylene protons in complexes of diethylsulfide.

The stereochemistry of thioether complexes have been extensively studied.[5] Unsymmetrical thioethers, e.g., SMeEt, are prochiral ligands, and their complexes are chiral. One example is [Ru(NH3)5(SMeEt)]2+. The complex cis-VOCl2(SMeEt)2 exists as meso- and a pair of enantiomers.[6] In complexes of thioethers of the type S(CH2R)2 (R ≠ H), the methylene protons are diastereotopic. Examination of the NMR spectra of such complexes reveal that they undergo inversion at sulfur, without dissociation of the M-S bond.[7]

Thioether as a bridging ligand

Unlike ethers, thioethers occasionally serve as bridging ligands. The complexes Nb2Cl6(SMe2)3 is one such example. It adopts a face-sharing bioctahedral structure with a Nb(III)=Nb(III) bond, spanned by two chloride and one dimethylsulfide ligands.[8] The complex Pt2Me4(SMe2)2 is a source of "PtMe2".[9] Geoffrey S. Hill Michael J. Irwin Christopher J. Levy Louis M. Rendina Richard J. Puddephatt volume 32 1998 149

Complexes thiacrown ligands

The tridentate tri-thioether 9-ane-S3 forms extensive families of complexes of the type M(9-ane-S3)L3 and [M(9-ane-S3)2]2+. Examples of Cu(II)-thioether complexes were prepared from 14-ane-S4[10] and 15-ane-S5.[11] The hexadentate ligand 18-ane-6 also forms extensive family of complexes, including unsual examples of Pd(III) and Ag(II).[12] Examples of homoleptic complexes [M(SR2)6]n+ are otherwise rare.

Structure of [Ag(18-ane-S6)]2+. The Ag-S distances are 2.62 Å.
Structure of [Ru(15-ane-5)Cl]+.[13]

References

  1. ^ Murray, Stephen G.; Hartley, Frank R. (1981). "Coordination chemistry of thioethers, selenoethers, and telluroethers in transition-metal complexes". Chemical Reviews. 81 (4): 365–414. doi:10.1021/cr00044a003.
  2. ^ Lever, A. B. P. (1990). "Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/Ruthenium(II) couple to generate a ligand electrochemical series". Inorganic Chemistry. 29 (6): 1271–1285. doi:10.1021/ic00331a030.
  3. ^ Krogh-Jespersen, Karsten; Zhang, Xiaohua; Ding, Yanbo; Westbrook, John D.; Potenza, Joseph A.; Schugar, Harvey J. (1992). "Molecular and Electronic Structures of Pentaammineruthenium(II)-Thioether Complexes. The Nature of Ru(II)-S Back Bonding Elucidated by Structural, Electronic Spectral, and Molecular Orbital Studies". Journal of the American Chemical Society. 114 (11): 4345–4353. doi:10.1021/ja00037a047.
  4. ^ [[cite journal|last1=Iijima|first1=T.|last2=Tsuchiy| first2=S.|last3=Kimura|first3=M.|title=The Molecular Structure of Dimethyl Sulfide|journal=Bull. Chem. Soc. Jpn.|year=1977|volume=50|page=2564|doi=10.1246/bcsj.50.2564}}
  5. ^ Abel, Edward W.; Bhargava, Suresh K.; Orrell, Keith G. (2007). "The Stereodynamics of Metal Complexes of Sulfur-, Selenium-, and Tellurium-Containing Ligands". Progress in Inorganic Chemistry: 1–118. doi:10.1002/9780470166338.ch1.
  6. ^ Matsuura, Masatoshi; Fujihara, Takashi; Nagasawa, Akira (2013). "Cis-Dichloridobis(ethyl methyl sulfide-κS)oxidovanadium(IV)". Acta Crystallographica Section e Structure Reports Online. 69 (4): m209. doi:10.1107/S1600536813006703. PMC 3629486. PMID 23634004.
  7. ^ Turley, Patricia C.; Haake, Paul. (1967). "Proton Magnetic Resonance Epectra of Platinum(II) Complexes. II. Cis- and trans- Bis(dialkyl sulfide)dichloroplatinum(II) Complexes. Mechanism of Inversion at Sulfur and Vicinal Platinum-Proton Couplings". Journal of the American Chemical Society. 89 (18): 4617–4621. doi:10.1021/ja00994a009.
  8. ^ . doi:10.1107/S1600536806005149. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
  9. ^ . doi:10.1002/9780470132630.ch25. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
  10. ^ . doi:10.1021/ic00166a033. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
  11. ^ . doi:10.1016/j.ica.2010.08.021. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
  12. ^ . doi:10.1021/ja0636439. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
  13. ^ . doi:10.1016/j.ica.2010.08.021. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help)
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