Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cobalt-dinitrogen complexes with weakened N-N bonds.

ABSTRACT: Reported N(2) complexes of cobalt do not have substantial weakening of the N-N bond. Using diketiminate ligands to enforce three-coordinate geometries, we have synthesized several novel CoNNCo complexes. In formally univalent complexes, cobalt is poorer than iron at weakening the N-N bond, but in formally zerovalent complexes, cobalt and iron give similar N-N weakening. The weakening is due to cobalt-to-N(2) pi-backbonding, and potassium cations pull more electron density into N(2). These results show that the low coordination number of a trigonal-planar geometry is impetus enough to make even the electronegative cobalt weaken the N-N bond of N(2).

SUBMITTER: Ding K

PROVIDER: S-EPMC2746749 | biostudies-literature | 2009 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cobalt-dinitrogen complexes with weakened N-N bonds.

Ding Keying K Pierpont Aaron W AW Brennessel William W WW Lukat-Rodgers Gudrun G Rodgers Kenton R KR Cundari Thomas R TR Bill Eckhard E Holland Patrick L PL

Journal of the American Chemical Society 20090701 27

Reported N(2) complexes of cobalt do not have substantial weakening of the N-N bond. Using diketiminate ligands to enforce three-coordinate geometries, we have synthesized several novel CoNNCo complexes. In formally univalent complexes, cobalt is poorer than iron at weakening the N-N bond, but in formally zerovalent complexes, cobalt and iron give similar N-N weakening. The weakening is due to cobalt-to-N(2) pi-backbonding, and potassium cations pull more electron density into N(2). These result ...[more]

PMID: 19537787

Similar Datasets

Cobalt-Magnesium and Iron-Magnesium Complexes with Weakened Dinitrogen Bridges.

Project description:The cooperative binding of N2 by late transition metals and main-group metals is a promising strategy for N-N bond weakening and activation. We report the use of activated Rieke magnesium for reduction of iron and cobalt complexes supported by bulky β-diketiminate ligands. Binding of N2 is accompanied by assembly of a linear M-NN-Mg-NN-M (M = Co, Fe) core with N-N bonds that are weakened, as judged by infrared spectroscopy. Both the cobalt and iron complexes require THF solvent, because of Mg-THF binding. The cobalt complex can be isolated as a pure solid, but the iron complex is stable only in solution. These results demonstrate the correlation between the binding mode and N-N weakening in heterobimetallic N2 complexes.

| S-EPMC3869404 | biostudies-literature

Three-coordinate and four-coordinate cobalt hydride complexes that react with dinitrogen.

Project description:We report the formation and N(2) reactivity of novel cobalt hydride complexes supported by bulky beta-diketiminate ligands (L). Addition of KHBEt(3) to LCoCl gives [LCo(mu-H)](2) (1) or K(2)[LCoH](2) (2), depending on the amount of borohydride used. Compound 2 is the first example of a crystallographically characterized hydride complex in which a transition metal is three-coordinate. Both 1 and 2 react with N(2) at room temperature to give dinuclear N(2) complexes with loss of H(2).

| S-EPMC2737074 | biostudies-literature

Side-On Bonded Beryllium Dinitrogen Complexes.

Project description:The preparation and spectroscopic identification of the complexes NNBe(?2 -N2 ) and (NN)2 Be(?2 -N2 ) and the energetically higher lying isomers Be(NN)2 and Be(NN)3 are reported. NNBe(?2 -N2 ) and (NN)2 Be(?2 -N2 ) are the first examples of covalently side-on bonded N2 adducts of a main-group element. The analysis of the electronic structure using modern methods of quantum chemistry suggests that NNBe(?2 -N2 ) and (NN)2 Be(?2 -N2 ) should be classified as ? complexes rather than metalladiazirines.

| S-EPMC7317369 | biostudies-literature

Dinitrogen complexes of sulfur-ligated iron.

Project description:We report a unique class of dinitrogen complexes of iron featuring sulfur donors in the ancillary ligand. The ligands utilized are related to the recently studied tris(phosphino)silyl ligands (2-R(2)PC(6)H(4))(3)Si (R = Ph, iPr) but have one or two phosphine arms replaced with thioether donors. Depending on the number of phosphine arms replaced, both mononuclear and dinuclear iron complexes with dinitrogen are accessible. These complexes contribute to a desirable class of model complexes that possess both dinitrogen and sulfur ligands in the immediate iron coordination sphere.

| S-EPMC3115625 | biostudies-literature

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes.

Project description:Dinitrogen (N2 ) is the most abundant gas in Earth's atmosphere, but its inertness hinders its use as a nitrogen source in the biosphere and in industry. Efficient catalysts are hence required to ov. ercome the high kinetic barriers associated to N2 transformation. In that respect, molecular complexes have demonstrated strong potential to mediate N2 functionalization reactions under mild conditions while providing a straightforward understanding of the reaction mechanisms. This Review emphasizes the strategies for N2 reduction and functionalization using molecular transition metal and actinide complexes according to their proposed reaction mechanisms, distinguishing complexes inducing cleavage of the N≡N bond before (dissociative mechanism) or concomitantly with functionalization (associative mechanism). We present here the main examples of stoichiometric and catalytic N2 functionalization reactions following these strategies.

| S-EPMC7986120 | biostudies-literature

Enantioselective Borylation of Aromatic C-H Bonds with Chiral Dinitrogen Ligands.

Project description:The borylation of C-H bonds catalyzed by transition metals has been investigated extensively in the past two decades, but no iridium-catalyzed enantioselective borylation of C-H bonds has been reported. We report a set of iridium-catalyzed enantioselective borylations of aromatic C-H bonds. This reaction relies on a set of newly developed chiral quinolyl oxazoline ligands. This process proceeds under mild conditions with good to excellent enantioselectivity, and the borylated products can be converted to enantioenriched derivatives containing new C-O, C-C, C-Cl, or C-Br bonds.

| S-EPMC5852249 | biostudies-literature

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand.

Project description:Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase.

| S-EPMC4961768 | biostudies-literature

Catalytic Silylation of Dinitrogen by a Family of Triiron Complexes.

Project description:A series of triiron complexes supported by a tris(?-diketiminate)cyclophane (L 3- ) catalyze the reduction of dinitrogen to tris(trimethylsilyl)amine using KC8 and Me3SiCl. Employing Fe3Br3 L affords 83 ± 7 equiv. NH4 +/complex after protonolysis, which is a 50% yield based on reducing equivalents. The series of triiron compounds tested evidences the subtle effects of ancillary donors, including halides, hydrides, sulfides, and carbonyl ligands, and metal oxidation state on N(SiMe3)3 yield, and highlight Fe3(?3-N)L as a common species in product mixtures. These results suggest that ancillary ligands can be abstracted with Lewis acids under reducing conditions.

| S-EPMC6296492 | biostudies-literature

Cation assisted binding and cleavage of dinitrogen by uranium complexes.

Project description:The role of alkali promoters in N2 cleavage by metal complexes remains poorly understood despite its relevance to the industrial production of ammonia from N2. Here we report a series of alkali bound-oxo-bridged diuranium(iii) complexes that provide a unique example of decreasing N2 binding affinity with increasing cation size (from K to Cs). N2 binding was found to be irreversible in the presence of K. A N2 complex could be isolated in the solid state in the presence of the Rb cation and crystallographically characterized, but N2 binding was found to be reversible under vacuum. In the presence of the Cs cation N2 binding could not be detected at 1 atm. Electrochemical and Computational studies suggest that the decrease in N2 binding affinity is due to steric rather than electronic effects. We also find that weak N2 binding in ambient conditions does not prevent alkali assisted N2 cleavage to nitride from occurring. More importantly, we present the first example of cesium assisted N2 cleavage leading to the isolation of a N2 derived multimetallic U/Cs bis-nitride. The nitrides readily react with protons and CO to yield ammonia, cyanate and cyanide.

| S-EPMC9384805 | biostudies-literature

Silylamido supported dinitrogen heterobimetallic complexes: syntheses and their catalytic ability.

Project description:Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(Me3Si)N]3MoN2Mg(THF)2[N(SiMe3)Ar] (5) and [Ar(Me3Si)N]3MoN2SiMe3 (6) (Ar = 3,5-Me2C6H3) were synthesized and structurally characterized, and proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. The 1H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating possible catalytic ability of the Mo-N=N motif.

| S-EPMC8694672 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data