Supramolecular coordination complexes of the N-thiophosphorylated 2,5-dithiobiurea [NHC(S)NHP(S-(OiPr)2]2 with Zn(II) and Cd(II): Cation induced dinuclear mesocate structure versus tetranuclear nanoscaled aggregate

Safin, Damir;Babashkina, Maria;Kubisiak, P.;Mitoraj, M.P.;Garcia, Yann;et.al.
(2014) European Journal of Inorganic Chemistry — Vol. 32, p. 5522-5529 (2014)

Files

5522_ftp.pdf
  • Restricted Access
  • Adobe PDF
  • 5.62 MB
Request a copy

Details

Authors
  • Safin, DamirUCLouvain
    Author
  • Babashkina, MariaUCLouvain
    Author
  • Kubisiak, P.Jagiellonian University, Cracow (Poland)
    Author
  • Mitoraj, M.P.Jagiellonian University, Cracow (Poland)
    Author
  • Le Duff, Cécile S.UCLouvain
    Author
  • Robeyns, KoenUCLouvain
    Author
  • Garcia, Yannorcid-logoUCLouvain
    Author
Show more
Abstract
The reaction of the deprotonated N-thiophosphorylated bisthiourea N,N-bis(diisopropoxythiophosphorylamidothiocarbonyl)hydrazine {[NHC(S)NHP(S)(OiPr)2]2, H2L} with ZnCl2 leads to the complex [Zn2{[NHC(S)NP(S)(OiPr)2]2}2] ([Zn2L2]), in which two metal cations are each 1,5-S,S-coordinated through the sulfur atoms of the thiocarbonyl and thiophosphoryl groups of the pendant deprotonated thioacylamidothiophosphate functions. The same reaction with CdCl2 leads to the tetranuclear nanoscaled aggregate [(Cd2{[NC(S)NHP(S)(OiPr)2]2}2)2] ([(Cd2L2)2]). This complex contains ligands that are doubly deprotonated through their hydrazine NH groups and exhibit unprecedented μ4 and μ5 coordination modes. DFT calculations have shown that both complexes are stabilized not only by typical coordination bonds (Zn–S, Cd–S) but also by numerous intramolecular “noncovalent” interactions: polar C–H···S and N–H···S, nonpolar C–H···H–C, and σ-hole bonding (S···S).
Affiliations

Citations

  • APA
  • Chicago
  • FWB

Safin, D., Babashkina, M., Kubisiak, P., Mitoraj, M. P., Le Duff, C. S., Robeyns, K., & Garcia, Y. (2014). Supramolecular coordination complexes of the N-thiophosphorylated 2,5-dithiobiurea [NHC(S)NHP(S-(OiPr)2]2 with Zn(II) and Cd(II): Cation induced dinuclear mesocate structure versus tetranuclear nanoscaled aggregate. European Journal of Inorganic Chemistry, 32, 5522-5529. https://doi.org/10.1002/ejic.201402544 (Original work published 2014)