Solvent-dependent reversible ligand exchange in nickel complexes of a monosulfide bis(diphenylphosphino)(N-thioether)amine

Alessio Ghisolfi, Christophe Fliedel, Vitor Rosa, Roberto Pattacini, Aurore Thibon, Kirill Yu Monakhov, Pierre Braunstein

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19 Citations (Scopus)


The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)(N-thioether)amine N(PPh2)2(CH 2)3SMe (1) and its monosulfide derivative, (Ph 2P)N{P(S)Ph2}(CH2)3SMe (1×S), towards NiII precursors has been investigated. The crystal structures of N{P(S)Ph2}2(CH2)3SMe (1×S2), [NiCl2{(Ph2P) 2N(CH2)3SMe-P,P}] (2), [NiCl 2((Ph2P)N{P(S)Ph2}(CH2) 3SMe-P,S)] (3), [Ni((Ph2P)N{P(S)Ph2}(CH 2)3SMe-P,S)2]NiCl4 (3'), [Ni((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S) 2](BF4)2 (4), and [Ni((Ph2P)NH{P(S) Ph2}-P,S)2]Cl2 (5) have been determined by single-crystal X-ray diffraction. In all of the complexes with the hybrid ligand 1×S, P,S-chelation to the NiII center is observed. Despite the stability generally associated with five-membered ring chelation, easy migration of this LL'-type P,S-chelating ligand from one metal center to another was observed, which accounts for the reversible ligand-redistribution reaction occurring in the equilibrium between the neutral, diamagnetic complex [NiCl 2LL'] and the paramagnetic ion-pair [Ni(LL')2][NiCl 4]. Detailed investigations by multinuclear NMR, UV/Vis, and FTIR spectroscopic methods and DFT calculations are reported. Each of the formula isomers 3 and 3' can be selectively obtained, depending on the experimental conditions. Swap deal: Easy migration of a P,S-chelating ligand to form five-membered rings in NiII complexes accounts for the reversible ligand redistribution that occurs in the equilibrium between the neutral complex [NiCl2LL'] and the ion-pair [Ni(LL')2][NiCl4].

Original languageEnglish
Pages (from-to)1795-1805
Number of pages11
JournalChemistry - An Asian Journal
Issue number8
Publication statusPublished - 1 Aug 2013


  • chelates
  • ligand exchange
  • nickel
  • short-bite ligands
  • solvent effects


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