A Salt Metathesis Route To Ruthenium Carbene Complex Isomers With Pyridine Dicarboxamide-Derived Chelate Pincer Ligands

Reaction of the doubly deprotonated pyridine 2,6-dicarboxamido ligand (1) with (PCy_3)_2Cl_2 Ru=CHPh (3a) in THF gave a mixture of (lig)(PCy_3)Ru=CHPh isomers (4). The pentane soluble N,N,O-4 isomer was isolated by extraction and characterized by X-ray diffraction. The O,N, O-4 isomer was identified in the residue. Single crystals of the closely related complex (lig)(NHC) Ru=CHPh, O,N,O-5, were obtained from the reaction of 1 with (NHC)(PCy_3)Cl_2Ru=CHPh (3b) and used for the X-ray crystal structure analysis of the system

Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs

Frustrated Lewis pairs comprising phosphine and borane react to reversibly bind and release CO2, offering a rare example of metal-free CO2 sequestration. The mechanism of formation of CO2 derivatives by almost simultaneous P-C and O-B bond formation was characterized by quantum chemical calculations

New insights into frustrated Lewis pairs: structural investigations of intramolecular phosphane-borane adducts by using modern solid-state NMR techniques and DFT calculations

Covalent bonding interactions between the Lewis acid and Lewis base functionalities have been probed in a series of “frustrated Lewis pairs” (FLPs) (mainly substituted vinylene linked intramolecular phosphane–borane adducts), using solid-state nuclear magnetic resonance techniques and accompanying DFT calculations. Both the 11B NMR isotropic chemical shifts and nuclear electric quadrupolar coupling parameters turn out to be extremely sensitive experimental probes for such interactions, revealing linear correlations with boron–phosphorus internuclear distances. The principal component Vzz of the 11B electric field gradient tensor is tilted slightly away (∼20°) from the boron–phosphorus internuclear vector, leading to an improved understanding of the remarkable reactivity of the FLPs. Complementary 31P{1H}-CPMAS experiments reveal significant 31P–11B scalar spin–spin interactions (1J ≈ 50 Hz), evidencing covalent bonding interactions between the reaction centers. Finally, 11B{31P} rotational echo double resonance (REDOR) experiments show systematic deviations from calculated curves based on the internuclear distances from X-ray crystallography. These deviations suggest non-zero contributions from anisotropic indirect spin–spin (J anisotropy) interactions, thereby offering additional evidence for covalent bonding.SFB 858 “Cooperative Systems in Chemistry”Fonds der Chemischen IndustrieNRW Forschungsschule “Molecules and Materials

A Salt Metathesis Route To Ruthenium Carbene Complex Isomers With Pyridine Dicarboxamide-Derived Chelate Pincer Ligands

Reaction of the doubly deprotonated pyridine 2,6-dicarboxamido ligand (1) with (PCy_3)_2Cl_2 Ru=CHPh (3a) in THF gave a mixture of (lig)(PCy_3)Ru=CHPh isomers (4). The pentane soluble N,N,O-4 isomer was isolated by extraction and characterized by X-ray diffraction. The O,N, O-4 isomer was identified in the residue. Single crystals of the closely related complex (lig)(NHC) Ru=CHPh, O,N,O-5, were obtained from the reaction of 1 with (NHC)(PCy_3)Cl_2Ru=CHPh (3b) and used for the X-ray crystal structure analysis of the system

Binding of molecular magnesium hydrides to a zirconocene-enyne template

An enyne-zirconium complex stabilizes molecular magnesium hydride ('MG''H IND. 2') and even a molecular hydride, n'C IND. 4''H IND. 9''MG'H. These systems feature magnesium olefin "pi" complexation.Deutsche ForschungsgemeinschaftNRW Forschungsschule “Molecules and Materials