Solvent-Dependent Reversible Ligand Exchange in Nickel Complexes of a Monosulfide Bis(diphenylphosphino)(N-thioether)amine

Authors

  • Alessio Ghisolfi,

    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
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  • Dr. Christophe Fliedel,

    Corresponding author
    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
    2. Current Address: REQUIMTE, Departamento de Quimica, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, 2829-516 (Portugal)
    • Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322

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  • Dr. Vitor Rosa,

    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
    2. Current Address: REQUIMTE, Departamento de Quimica, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, 2829-516 (Portugal)
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  • Dr. Roberto Pattacini,

    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
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  • Dr. Aurore Thibon,

    1. Laboratoire de Chimie Biomimétique des Métaux de Transition, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France)
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  • Dr. Kirill Yu. Monakhov,

    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
    2. Current Address: Institut für Anorganische Chemie, RWTH-Aachen University, Landoltweg 1, 52074 Aachen (Germany)
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  • Prof. Pierre Braunstein

    Corresponding author
    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322
    • Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg (France), Fax: (+33) 368-851-322

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Abstract

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 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}] (), [NiCl2((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S)] (), [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 (), and [Ni((Ph2P)NH{P(S)Ph2}-P,S)2]Cl2 () 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 [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 and 3′ can be selectively obtained, depending on the experimental conditions.

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