Metal dinitrogen complexes

The most likely explanation for the lateness of the discovery of in vitro syntheses of dinitrogen —metal complexes is probably the dominance of the paradigm that N2 is an (almost) inert molecule. The influence of that paradigm (in the sense of Kuhn, 1962) on another scientific discovery was discussed in the book on aromatic diazo compounds (Zollinger, 1994, Chapt. 9). 

X-Ray structures are most informative on bonding in dinitrogen metal complexes. In addition, IR spectra are very useful, particularly on the basis of the NN stretching frequency. 

Dinitrogen-metal complexes can also act as simple donors to Lewis acids like AICI3 or A1(CH3)3 (Donovan-Mtunzi et al., 1985, and references therein). 

The enzymology and biochemistry of nitrogenases started only a few years before the first dinitrogen metal complex was discovered by Allen and Senoff in 1965. Cooperation and mutual encouragement increased when more and more results were found on both sides. Two iron-sulfur proteins are involved in the nitrogenase complex. The larger protein, the nitrogenase itself, consists of four subunits and has an... 

For the dinitrogen-metal complex either a mono- or binuclear complex (see Sect. 3.3) must be considered. Both types are well-known, and protonation has been investigated (mononuclear complexes Henderson et al., 1983, 1989 Shilov, 1992, and references therein binuclear complexes Dilworth et al., 1990 Henderson et al., 1990 Henderson and Morgan, 1990 Shilov, 1992 Blomberg and Siegbahn, 1993). In a review, Henderson (1990) illustrated the range of binuclear species that contain nitrogenous residues from the mono- to the tetra-protonated forms. 

Dinitrogen metal complexes can also be silylated at the N()0)-atom by treatment with suitable trialkylsilane derivatives. Such reactions were also investigated by... 

MacLachlan EA, Fryznk MD. Synthesis and reactivity of side-on-bound dinitrogen metal complexes. Organometallics. 2006 25 1530-1543. 

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). 

Metal complexes as inorganic nitrogen-fixing systems Fixation of molecular nitrogen and ammonia synthesis Complexes of dinitrogen... 

A remarkable process was reported by Mori that forms aniline from dinitrogen (Equation (26)).106 Titanium nitrogen fixation complexes were generated from reactions of titanium tetrachloride or tetraisopropoxide, lithium metal, TMS chloride, and dinitrogen. These complexes generated a mixture of aryl and diarylamines in yields as high as 80% when treated with aryl halide and a palladium catalyst containing DPPF ... 

THE REACTIVITY OF TRANSITION METAL COMPLEXES WITH DINITROGEN... 

Interest in metal complexes able to bind molecular dinitrogen is mainly due to a desire to understand and reproduce in the laboratory the so-called nitrogen fixation reaction. This process, which in nature is catalysed by the metalloprotein nitrogenases, reduces the inert dinitrogen molecule to the metabolically useful NH3 ... 

Metal Complexes with Terminal Coordination to One Dinitrogen Molecule... 

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

Selective and reversible adsorption of gaseous molecules such as dioxygen, carbon monoxide, ethylene, acetylene, and dinitrogen have been performed by the use of suitable macromolecule-metal complexes. Selective adsorption of metal ions such as UO has also been studied using polymeric ligands. 

---