Solvent-Dependent Reversible Ligand Exchange in Nickel Complexes of a Monosulfide Bis(diphenylphosphino)(N-thioether)amine
| Autor: | Christophe Fliedel, Alessio Ghisolfi, Pierre Braunstein, Aurore Thibon, Kirill Yu. Monakhov, Roberto Pattacini, Vitor Rosa |
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| Přispěvatelé: | Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2013 |
| Předmět: |
Phosphines
Stereochemistry Molecular Conformation chemistry.chemical_element Crystal structure Sulfides Crystallography X-Ray Ligands 010402 general chemistry 01 natural sciences Biochemistry Coordination complex chemistry.chemical_compound Thioether Coordination Complexes Nickel [CHIM.COOR]Chemical Sciences/Coordination chemistry ComputingMilieux_MISCELLANEOUS chemistry.chemical_classification Aniline Compounds 010405 organic chemistry Chemistry Ligand Organic Chemistry Center (category theory) General Chemistry 0104 chemical sciences Crystallography Solvents Solvent effects Phosphine |
| Zdroj: | Chemistry-An Asian Journal Chemistry-An Asian Journal, Wiley-VCH Verlag, 2013, 8 (8), pp.1795-1805. ⟨10.1002/asia.201300687⟩ |
| ISSN: | 1861-4728 1861-471X |
| DOI: | 10.1002/asia.201300687 |
| Popis: | The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)(N-thioether)amine N(PPh2)2(CH2)3SMe () and its monosulfide derivative, (Ph2P)N{P(S)Ph2}(CH2)3SMe (1·S), towards Ni(II) 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), [NiCl2((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S)] (3), [Ni((Ph2P)N{P(S)Ph2}(CH2)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 Ni(II) 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 [NiCl2LL'] and the paramagnetic ion-pair [Ni(LL')2][NiCl4]. 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. |
| Databáze: | OpenAIRE |
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