877169-14-7Relevant academic research and scientific papers
Catalytic nitrene transfer from an imidoiron(iii) complex to form carbodiimides and isocyanates
Cowley, Ryan E.,Eckert, Nathan A.,Elha?k, Jér?me,Holland, Patrick L.
, p. 1760 - 1762 (2009/08/08)
The metastable iron(iii) imido species LtBuFeNAd catalyzes transfer of the nitrene fragment NAd from an organic azide to isocyanides or CO, forming unsymmetrical carbodiimides or isocyanates. The Royal Society of Chemistry.
Reduction of CO2 to CO using low-coordinate iron: Formation of a four-coordinate iron dicarbonyl complex and a bridging carbonate complex
Sadique, Azwana R.,Brennessel, William W.,Holland, Patrick L.
, p. 784 - 786 (2008/10/09)
A reduced diiron(I) complex reacts with CO2 to give two iron-containing products. One product has a carbonate bridge, which isomerizes rapidly at -70°C and may be derived from an oxodiiron intermediate. The formation of this product releases free CO, which leads to a four-coordinate iron dicarbonyl complex. This product is the first crystallographically characterized example of a four-coordinate iron dicarbonyl species, a moiety that may be present in the active site of Hmd ( iron-sulfur cluster free ) hydrogenase.
Studies of low-coordinate iron dinitrogen complexes
Smith, Jeremy M.,Sadique, Azwana R.,Cundari, Thomas R.,Rodgers, Kenton R.,Lukat-Rodgers, Gudrun,Lachicotte, Rene J.,Flaschenriem, Christine J.,Vela, Javier,Holland, Patrick L.
, p. 756 - 769 (2007/10/03)
Understanding the interaction of N2 with iron is relevant to the iron catalyst used in the Haber process and to possible roles of the FeMoco active site of nitrogenase. The work reported here uses synthetic compounds to evaluate the extent of NN weakening in low-coordinate iron complexes with an FeNNFe core. The steric effects, oxidation level, presence of alkali metals, and coordination number of the iron atoms are varied, to gain insight into the factors that weaken the NN bond. Diiron complexes with a bridging N2 ligand, LRFeNNFeLR (LR = β-diketiminate; R = Me, tBu), result from reduction of [LRFeCl]n under a dinitrogen atmosphere, and an iron(I) precursor of an N2 complex can be observed. X-ray crystallographic and resonance Raman data for LRFeNNFeLR show a reduction in the N-N bond order, and calculations (density functional and multireference) indicate that the bond weakening arises from cooperative back-bonding into the N2 π* orbitals. Increasing the coordination number of iron from three to four through binding of pyridines gives compounds with comparable N-N weakening, and both are substantially weakened relative to five-coordinate iron-N 2 complexes, even those with a lower oxidation state. Treatment of LRFeNNFeLR with KC8 gives K2L RFeNNFeLR, and calculations indicate that reduction of the iron and alkali metal coordination cooperatively weaken the N-N bond. The complexes LRFeNNFeLR react as iron(I) fragments, losing N2 to yield iron(I) phosphine, CO, and benzene complexes. They also reduce ketones and aldehydes to give the products of pinacol coupling. The K2LRFeNNFeLR compounds can be alkylated at iron, with loss of N2.
