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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

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Safin, Damir [UCL] Babashkina, Maria [UCL] Kubisiak, P. [Jagiellonian University, Cracow (Poland)] Mitoraj, M.P. [Jagiellonian University, Cracow (Poland)] Le Duff, Cécile S. [UCL] Robeyns, Koen [UCL] Garcia, Yann [UCL]

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).

Document type Article de périodique (Journal article) – Article de recherche
Access type Accès restreint
Publication date 2014
Language Anglais
Journal information "European Journal of Inorganic Chemistry" - Vol. 32, p. 5522-5529 (2014)
Peer reviewed yes
Publisher Wiley - V C H Verlag GmbH & Co. KGaA ((Germany) Weinheim)
issn 1434-1948
e-issn 1099-0682
Publication status Publié
Affiliation UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity
Keywords Supramolecular chemistry / Nanostructures / Cadmium / Zinc / S ligands
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Bibliographic reference Safin, Damir ; Babashkina, Maria ; Kubisiak, P. ; Mitoraj, M.P. ; Le Duff, Cécile S. ; et. al. 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. In: European Journal of Inorganic Chemistry, Vol. 32, p. 5522-5529 (2014)
Permanent URL http://hdl.handle.net/2078.1/155341