Nitrido bridges between transition metals and main group elements illustrated by the series [M]NNa to [M]NCl

Abstract

A survey is given of the structures and bonding modes of nitrido bridges between transition metals with MN multiple bonds and main group elements. Illustrated by the period row sodium (I) to chlorine (VII) (or a homologue) along with variable transition metals M, characteristic examples are compiled, their principles of synthesis are presented and the step-by-step alterations of the bonding conditions that occur in this period are discussed on the basis of structural parameters. These bonding conditions can be divided into three groups.

(1)  Electrostatic bond between nitrido ligand and main group element (I, II)

(2)  Covalent single bond (III, IV)

(3)  Multiple bonds between both neighbouring elements (V–VII)

One example each is designed to illustrate this aim:

(i) Na₆[MoN₄];

(ii) [Mg(THF)₄{NMoCl₄(THF)}₂ ];

(iii) [ReN–GaCl₃(PMe₂Ph)(Et ₂dtc)₂] (no example with Al is known up to now);

(iv) Cl₃VN–SiMe₃;

(v) O₃ReNPMe₃;

(vi) [Cl₅WNSCl]⁻;

(vii) [F₅WNCl]⁻.