Ammonia is an important nutrient for the growth of plants. In industry, ammonia is produced by the energy expensive Haber-Bosch process where dihydrogen and dinitrogen form ammonia at a very high pressure and temperature. In principle one could also reduce dinitrogen upon addition of protons and electrons similar to the mechanism of ammonia production by nitrogenases. Recently, major breakthroughs have taken place in our understanding of biological fixation of dinitrogen, of molecular model systems that can reduce dinitrogen, and in the electrochemical reduction of dinitrogen at heterogeneous surfaces. Yet for efficient reduction of dinitrogen with protons and electrons major hurdles still have to be overcome. In this tutorial review we give an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen.

Unprecedented rhodium-catalyzed stereoselective polymerization of "carbenes" from ethyl diazoacetate (EDA) to give high molecular mass poly(ethyl 2-ylidene-acetate) is described. The mononuclear, neutral [(N,O-ligand)M(I)(cod)] (M = Rh, Ir) catalytic precursors for this reaction are characterized by (among others) single-crystal X-ray diffraction. These species mediate formation of a new type of polymers from EDA: carbon-chain polymers functionalized with a polar substituent at each carbon of the polymer backbone. The polymers are obtained as white powders with surprisingly sharp NMR resonances. Solution and solid state NMR data for these new polymers reveal a highly stereoregular polymer, with a high degree of crystallinity. The polymer is likely syndiotactic. Material properties are very different from those of atactic poly(diethyl fumarate) polymer obtained by radical polymerization of diethyl fumarate. Other diazoacetates are also polymerized. Further studies are underway to reveal possible applications of these new materials.

DFT calculations show that square‐planar LCoIR complexes of a diiminopyridine ligand are best regarded as containing low‐spin CoII antiferromagnetically coupled to a ligand radical anion. The lowest triplet state, corresponding to a 3d italicz 2⇄π* excitation, is calculated to be only a few kcal/mol above the ground state, and is thermally accessible. The anomalous 1H NMR chemical shifts of the LCoR complexes are suggested to be due to thermal population of the triplet state at room temperature. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Catalytic pathwaysfor the reduction of dioxygen can either lead to the formation of water or peroxide as the reaction product. We demonstrate that the electrocatalytic reduction of O 2 by the pyridylalkylamine copper complex [Cu(tmpa)(L)] 2+ in an eutral aqueous solution follows as tepwise 4e À /4 H + pathway,inwhich H 2 O 2 is formed as adetectable intermediate and subsequently reduced to H 2 Oi nt wo separate catalytic reactions.These homogeneous catalytic reactions are shown to be first order in catalyst. Coordination of O 2 to Cu I was found to be the rate-determining step in the formation of the peroxide intermediate.F urthermore,e lectrochemical studies of the reaction kinetics revealed ah igh turnover frequency of 1.5 10 5 s À1 ,the highest reported for any molecular copper catalyst.

Me(2)-NHC proved to be a valuable ligand in iridium catalyzed water oxidation reactions, both when carried out electrochemically as well as upon oxidation with cerium ammonium nitrate. Mechanistic data suggest that water oxidation occurs efficiently at a well defined iridium species via a mononuclear pathway.

Recently, several mononuclear water oxidation catalysts have been reported, a breakthrough considering the dogma that at least two metal sites were required to oxidize water efficiently. In this Review various mononuclear catalysts which have been reported in the last five years are reviewed, as well as their implementation in prototype devices that allow dioxygen formation to be coupled to dihydrogen production will be discussed.

One-electron oxidation of [(Me(n)tpa)Ir(I)(ethene)]+ complexes (Me(3)tpa = N,N,N-tri(6-methyl-2-pyridylmethyl)amine; Me(2)tpa = N-(2-pyridylmethyl)-N,N,-di[(6-methyl-2-pyridyl)methyl]-amine) results in relatively stable, five-coordinate Ir(II)-olefin species [(Me(n)tpa)Ir(II)(ethene)](2+) (1(2+): n = 3; 2(2+): n = 2). These contain a "vacant site" at iridium and a "non-innocent" ethene fragment, allowing radical type addition reactions at both the metal and the ethene ligand. The balance between metal- and ligand-centered radical behavior is influenced by the donor capacity of the solvent. In weakly coordinating solvents, 1(2+) and 2(2+) behave as moderately reactive metallo-radicals. Radical coupling of 1(2+) with NO in acetone occurs at the metal, resulting in dissociation of ethene and formation of the stable nitrosyl complex [(Me(3)tpa)Ir(NO)](2+) (6(2+)). In the coordinating solvent MeCN, 1(2+) generates more reactive radicals; [(Me(3)tpa)Ir(MeCN)(ethene)](2+) (9(2+)) by MeCN coordination, and [(Me(3)tpa)Ir(II)(MeCN)](2+) (10(2+)) by substitution of MeCN for ethene. Complex 10(2+) is a metallo-radical, like 1(2+) but more reactive. DFT calculations indicate that 9(2+) is intermediate between the slipped-olefin Ir(II)(CH(2)=CH(2)) and ethyl radical Ir(III)-CH(2)-CH(2). resonance structures, of which the latter prevails. The ethyl radical character of 9(2+) allows radical type addition reactions at the ethene ligand. Complex 2(2+) behaves similarly in MeCN. In the absence of further reagents, 1(2+) and 2(2+) convert to the ethylene bridged species [(Me(n)tpa)(MeCN)Ir(III)(mu(2)-C(2)H(4))Ir(III)(MeCN)(Me(3)tpa)](4+) (n = 3: 3(4+); n = 2: 4(4+)) in MeCN. In the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxo), formation of 3(4+) from 1(2+) in MeCN is completely suppressed and only [(Me(3)tpa)Ir(III)(TEMPO(-))(MeCN)](2+) (7(2+)) is formed. This is thought to proceed via radical coupling of TEMPO at the metal center of 10(2+). In the presence of water, hydrolysis of the coordinated acetonitrile fragment of 7(2+) results in the acetamido complex [(Me(3)tpa)Ir(III)(NHC(O)CH(3)))(TEMPOH)](2+) (8(2+)).

We present a systematic electrochemical and spectroelectrochemical study of the catalytic activity for water oxidation of an iridium-N-dimethylimidazolin-2-ylidene (Ir-NHC-Me2) complex adsorbed on a polycrystalline gold electrode. The work aims to understand the effect of the electrolyte properties (anions and acidity) on the activity of the molecular catalyst and check its stability toward decomposition. Our results show that the iridium complex displays a very strong dependence on the electrolyte properties such that large enhancements in catalytic activity may be obtained by adequately choosing pH and anions in the electrolyte. The stability of the adsorbed compound was investigated in situ by Surface Enhanced Raman Spectroscopy and Online Electrochemical Mass Spectrometry showing that the catalyst exhibits good stability under anodic conditions, with no observable evidence for the decomposition to iridium oxide.