Publication
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}(mu-eta 1:eta 1-N2)(M{N(SiMe3)2}3)], 1-M (M = U(iii), Ce(iii), Sm(iii), Dy(iii) and Tm(iii)), [{Fe(depe)2}(mu-eta 1:eta 1-N2)(Ln{N(SiMe3)2}2)], 1*-Ln (Ln = Sm(ii), Yb(ii)) and [{Fe(depe)2(mu-eta 1:eta 1-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.|End-on bridging dinitrogen binding to U(iii), Ln(iii) and Ln(ii) is favoured for the iron-bound N2 compared to free N2, resulting in increased N2 activation with increasing Ln Lewis acidity with a back-bonding contribution only found for U(iii).