Syntheses of N2-bridged heterobimetallic complexes, their structural and qualitative bonding analyses

A series of N2-bridged (mu-eta 1:eta 1-N2) heterobimetallic complexes were prepared by the reaction of the dinitrogen complex [Mo(depe)2(N2)2] (depe = 1,2-bis(diethylphosphino)ethane) with the group IV-VI high valent metal halides [Cp2ZrCl2], NbCl5, TaCl5, MoCl5 and WCl4 via chloride substitution. Compounds [MoCl(depe)2(mu-N2)ZrCp2Cl] ( 1 ) and [MoCl(depe)2(mu-N2)M'Cl4(THF)] ( 2 -5 , M' = Nb, Ta, Mo or W) were crystallized from the reaction mixtures. In the case of the reaction with WCl4, disproportionation of W(IV) was suspected but not evidenced. Single crystal X-ray diffraction analyses on all compounds allowed a systematic structural study, and the sketching of qualitative molecular orbital diagrams helped discussing the bonding situation and bolster the structural data.(c) 2022 Elsevier B.V. All rights reserved.

Automated summary

A series of N2-bridged heterobimetallic complexes were prepared by reacting the dinitrogen complex [Mo(depe)2(N2)2] with group IV-VI high valent metal halides via chloride substitution. Crystallization of the reaction mixtures yielded compounds [MoCl(depe)2(mu-N2)ZrCp2Cl] and [MoCl(depe)2(mu-N2)M'Cl4(THF)], where M' = Nb, Ta, Mo, or W. Single crystal X-ray diffraction analyses provided insights into the structural features of these complexes, and qualitative molecular orbital diagrams were used to discuss the bonding situation.