Artículo
Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides
Autor/es | Jori, Nadir
Moreno Díaz, Juan José ![]() ![]() ![]() ![]() ![]() Shivaraam, R. A.Keerthi Rajeshkumar, Thayalan Scopelliti, Rosario Maron, Laurent Mazzanti, Marinella |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2024-04-02 |
Fecha de depósito | 2024-05-28 |
Publicado en |
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Resumen | End-on binding of dinitrogen to low valent metal centres is common in transition metal chemistry but
remains extremely rare in f-elements chemistry. In particular, heterobimetallic end-on N2 bridged
complexes of lanthanides ... End-on binding of dinitrogen to low valent metal centres is common in transition metal chemistry but remains extremely rare in f-elements chemistry. In particular, heterobimetallic end-on N2 bridged complexes of lanthanides are unprecedented despite their potential relevance in catalytic reduction of dinitrogen. Here we report the synthesis and characterization of a series of N2 bridged heterobimetallic complexes of U(III), Ln(III) and Ln(II) which were prepared by reacting the Fe dinitrogen complex [Fe(depe)2(N2)] (depe = 1,2-bis(diethylphosphino)-ethane), complex A with [MIII{N(SiMe3)2}3] (M = U, Ce, Sm, Dy, Tm) and [LnII{N(SiMe3)2}2], (Ln = Sm, Yb). Despite the lack of reactivity of the U(III), Ln(III) and Ln(II) amide complexes with dinitrogen, the end-on dinitrogen bridged heterobimetallic complexes [{Fe(depe)2}(m-h1 :h1 -N2)(M{N(SiMe3)2}3)], 1-M (M = U(III), Ce(III), Sm(III), Dy(III) and Tm(III)), [{Fe(depe)2}(mh1 :h1 -N2)(Ln{N(SiMe3)2}2)], 1*-Ln (Ln = Sm(II), Yb(II)) and [{Fe(depe)2(m-h1 :h1 -N2)}2{SmII{N(SiMe3)2}2}], 3 could be prepared. The synthetic method used here allowed to isolate unprecedented end-on bridging N2 complexes of divalent lanthanides which provide relevant structural models for the species involved in the catalytic reduction of dinitrogen by Fe/Sm(II) systems. Computational studies showed an essentially electrostatic interaction of the end-on bridging N2 with both Ln(III) and Ln(II) complexes with the degree of N2 activation correlating with their Lewis acidity. In contrast, a back-bonding covalent contribution to the U(III)–N2Fe bond was identified by computational studies. Computational studies also suggest that end-on binding of N2 to U(III) and Ln(II) complexes is favoured for the iron-bound N2 compared to free N2 due to the higher N2 polarization. |
Agencias financiadoras | Swiss National Science Foundation (SNFS) European Commission (EC) |
Identificador del proyecto | 212723
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Cita | Jori, N., Moreno Díaz, J.J., Shivaraam, R.A.K., Rajeshkumar, T., Scopelliti, R., Maron, L. y Mazzanti, M. (2024). Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides. Chemical Science, 15 (18), 6842-6852. https://doi.org/10.1039/D4SC01050G. |
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