Catalytic conversion of nitrogen to ammonia by an iron model complex

The reduction of nitrogen (N_2) to ammonia (NH_3) is a requisite transformation for life. Although it is widely appreciated that the iron-rich cofactors of nitrogenase enzymes facilitate this transformation, how they do so remains poorly understood. A central element of debate has been the exact site or sites of N_2 coordination and reduction. In synthetic inorganic chemistry, an early emphasis was placed on molybdenum because it was thought to be an essential element of nitrogenases and because it had been established that well-defined molybdenum model complexes could mediate the stoichiometric conversion of N_2 to NH_3 (ref. 9). This chemical transformation can be performed in a catalytic fashion by two well-defined molecular systems that feature molybdenum centres. However, it is now thought that iron is the only transition metal essential to all nitrogenases, and recent biochemical and spectroscopic data have implicated iron instead of molybdenum as the site of N_2 binding in the FeMo-cofactor. Here we describe a tris(phosphine)borane-supported iron complex that catalyses the reduction of N_2 to NH_3 under mild conditions, and in which more than 40 per cent of the proton and reducing equivalents are delivered to N_2. Our results indicate that a single iron site may be capable of stabilizing the various N_xH_y intermediates generated during catalytic NH_3 formation. Geometric tunability at iron imparted by a flexible iron–boron interaction in our model system seems to be important for efficient catalysis. We propose that the interstitial carbon atom recently assigned in the nitrogenase cofactor may have a similar role, perhaps by enabling a single iron site to mediate the enzymatic catalysis through a flexible iron–carbon interaction

Low-Spin Pseudotetrahedral Iron(I) Sites in Fe_2(μ-S) Complexes

Fe^I centers in iron–sulfide complexes have little precedent in synthetic chemistry despite a growing interest in the possible role of unusually low valent iron in metalloenzymes that feature iron–sulfur clusters. A series of three diiron [(L_3Fe)_2(μ-S)] complexes that were isolated and characterized in the low-valent oxidation states Fe^(II) S Fe^(II), Fe^(II) S Fe^I, and Fe^I S Fe^I is described. This family of iron sulfides constitutes a unique redox series comprising three nearly isostructural but electronically distinct Fe_2(μ-S) species. Combined structural, magnetic, and spectroscopic studies provided strong evidence that the pseudotetrahedral iron centers undergo a transition to low-spin S=1/2 states upon reduction from Fe^(II) to Fe^I. The possibility of accessing low-spin, pseudotetrahedral Fe^I sites compatible with S^(2−) as a ligand was previously unknown

The probability density function tail of the Kardar-Parisi-Zhang equation in the strongly non-linear regime

An analytical derivation of the probability density function (PDF) tail describing the strongly correlated interface growth governed by the nonlinear Kardar-Parisi-Zhang equation is provided. The PDF tail exactly coincides with a Tracy-Widom distribution i.e. a PDF tail proportional to $\exp( - c w_2^{3/2})$, where $w_2$ is the the width of the interface. The PDF tail is computed by the instanton method in the strongly non-linear regime within the Martin-Siggia-Rose framework using a careful treatment of the non-linear interactions. In addition, the effect of spatial dimensions on the PDF tail scaling is discussed. This gives a novel approach to understand the rightmost PDF tail of the interface width distribution and the analysis suggests that there is no upper critical dimension.Comment: 17 pages, 2 figure

Conversion of Fe−NH_2 to Fe−N_2 with release of NH_3

Tris(phosphine)borane ligated Fe(I) centers featuring N_2H_4, NH_3, NH_2, and OH ligands are described. Conversion of Fe–NH_2 to Fe–NH_3^+ by the addition of acid, and subsequent reductive release of NH_3 to generate Fe–N_2, is demonstrated. This sequence models the final steps of proposed Fe–mediated nitrogen fixation pathways. The five-coordinate trigonal bipyramidal complexes described are unusual in that they adopt S = 3/2 ground states and are prepared from a four-coordinate, S = 3/2 trigonal pyramidal precursor