Dinitrogen transition metal complexes

In this chapter we discuss host-guest complexes of arenediazonium salts with crown ethers and related compounds. Transition metal complexes of arenediazonium ions are treated together with those of dinitrogen and of diazoalkanes in our second book (Zollinger, 1995, Sec. 10.1). 

Geometric and electronic factors of dinitrogen activation on transition metal complexes. P. Pelikan and R. Boca, Coord. Chem. Rev., 1984, 55, 55-112 (190). 

Dinitrogen-transition metal complexes synthesis, properties and significance. D. Sellmann, Angew. Chem., Int. Ed. Engl., 1974,13, 639-649 (86). 

THE REACTIVITY OF TRANSITION METAL COMPLEXES WITH DINITROGEN... 

The binding and reactivity of dinitrogen in transition metal complexe 718... 

Dihydrogen is evolved prior to reduction of dinitrogen, as exemplified by transition metal complexes [Eqs. (86) and (87)]. 

In view of the many approximations in these semi-empirical calculations their results can only be regarded as first hints for more elaborate methods. Such are DFT calculations on FeMoco-type clusters and model complexes. As it is discussed, for instance, in Ref. (31), N2 usually binds very weakly to transition metal complexes. It is thus not certain whether end-on coordination to one or two iron centers can lead to sufficiently strong coordination of dinitrogen. 

In addition to the classical Haber process, recent efforts have been directed to finding an alternative economic process for fixing N2 to meet-increasing demands for nitrogeneous fertilizers and others industrial requirements. Thus, numerous results of the recent advances in the Chemistry of Nitrogen Fixation via transition metal complexes have reported (Chatt et al. 1978 A treatise on dinitrogen fixation , Hardy ed. 1979 New trends in the chemistry of nitrogen fixation , Chatt ed.1980). 

Studies on model polynuclear catalytic systems have confirmed that for the catalytic reduction of dinitrogen under mild conditions, it is necessary to use a polynuclear transition metal complex capable of donating four electrons to form the hydrazine derivative. 

Scheme 2 Coordination of dinitrogen in transition metal complexes 3 ATOMIC NITROGEN...

Addition Products of Dinitrogen to Transition Metal Complexes... 

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