Experimental and theoretical study of non-covalent interactions in organometallic chemistry : the concept of hemichelation

Abstract : The present manuscript will present a rational method of synthesis, characterization, determination of the electronic structure and dynamic behaviour of solution-persistent, and formally unsaturated binuclear Cr(0)-M complexes (with M= Pd(II), Pt(II) or Rh(I)). This new class of complexes constitutes rare examples of persistent coordinatively unsaturated 14-electrons complexes, whose cohesion stems essentially from a compensation of insufficient donor/acceptor Cr-M bonding by non-covalent interactions of preponderant attractive Coulombic nature. By taking advantage of the ambiphilic character of a heteroditopic ligand capable of chelating a metal centre through covalent and noncovalent bonds, truly coordination-unsaturated complexes can be synthesized in a manageable form. We propose to name “Hemichelation” the half-covalent/half noncovalent bonding-relationship between the ambiphilic heteroditopic ligand and the electron-unsaturated metallic centre.
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Christophe Werlé. Experimental and theoretical study of non-covalent interactions in organometallic chemistry : the concept of hemichelation. Other. Université de Strasbourg, 2014. English. ⟨NNT : 2014STRAF032⟩. ⟨tel-01249392⟩

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