RESUMEN
Because of the continually rising levels of CO2 in the atmosphere, research for the conversion of CO2 into fuels using carbon-neutral energy is an important and current topic in catalysis. Recent research on molecular catalysts has led to improved rates for conversion of CO2 to formate, but the catalysts are based on precious metals such as iridium, ruthenium and rhodium and require high temperatures and high pressures. Using established thermodynamic properties of hydricity (ΔGH(-)) and acidity (pKa), we designed a cobalt-based catalyst system for the production of formate from CO2 and H2. The complex Co(dmpe)2H (dmpe is 1,2-bis(dimethylphosphino)ethane) catalyzes the hydrogenation of CO2, with a turnover frequency of 3400 h(-1) at room temperature and 1 atm of 1:1 CO2:H2 (74,000 h(-1) at 20 atm) in tetrahydrofuran. These results highlight the value of fundamental thermodynamic properties in the rational design of catalysts.
RESUMEN
An organometallic building block strategy was employed to investigate the magnetic properties of a Ln(III) organometallic single-ion magnet (SIM) and subsequent single-molecule magnet (SMM) after coupling two of the monomeric units. New homoleptic Dy(III)COTâ³2 and Ln(III)2COTâ³3 (Ln = Gd, Dy) complexes have been synthesized. DFT calculations of the bimetallic Dy(III) complex indicate strong metal-ligand covalency and uneven donation to the Dy(III) ions by the terminal and internal COTâ³(2-) (cyclooctatetraenide) rings that correlate with the respective bond distances. Interestingly, the studies also point to a weak covalent interaction between the metal centers, despite a large separation. The ac susceptibility data indicates that both Dy(III)COTâ³2 and Dy(III)2COTâ³3 act as an SIM and an SMM, respectively, with complex multiple relaxation mechanisms. Ab initio calculations reveal the direction of the magnetic anisotropic axis is not perpendicular to the planar COTâ³ rings for both Dy(III)COTâ³2 and Dy(III)2COTâ³3 complexes due to the presence of trimethylsilyl groups on the COTâ³ rings. If these bulky groups are removed, the calculations predict reorientation of the anisotropic axis can be achieved.
RESUMEN
A tetralithio salt (1) derived by treating 1,4-bis(trimethylsilyl)-cyclooctatriene with (n)BuLi serves as the first structural evidence for a multi-alkali metallocene. Single-crystal XRD confirms two Li(+) each asymmetrically bind to η(3) and η(4) between two COT'' rings and two Li(+) terminally bind to η(3). Solid-state NMR studies confirm the presence of two distinct lithium ion sites while the solution NMR studies suggest the formation of an (COT'' dianion) ion-pair in solution. Further treating of the tetralithio salt with NaCl leads to linear sodium polymeric chains. Therefore, simply changing the ionic radius changes the molecular structure.
RESUMEN
A dysprosium(III) sandwich complex, [Dy(III)(COTâ³)(2)Li(THF)(DME)], was synthesized using 1,4-bis(trimethylsilyl)cyclooctatetraenyl dianion (COTâ³). The complex behaves as a single-ion magnet and demonstrates unusual multiple relaxation modes. The observed relaxation pathways strongly depend on the applied static dc fields.
RESUMEN
This report details the synthesis and characterization of the first chiral diNHC cyclophane ligand and its palladium allyl complex. The complex was tested for 1,4-conjugate addition of phenylboronic acid to 2-cyclohexen-1-one and provides R-3-phenylcyclohexanone in 50% enantiomeric excess.
RESUMEN
New iridium and rhodium complexes prepared from C2-symmetric trans-9,10-dihydro-9,10-ethanoanthracene-11,12-bis(1-R)-benzimidazolidine-2-ylidene ligands (R=Me, iPr, and diPh) have been synthesized and characterized. Their catalytic activities have been tested in enantioselective hydrogenation and hydroformylation reactions. The ee's for the reactions are low. Evidence indicates that even chelating di-N-heterocyclic carbene ligands are susceptible to reductive elimination.