Stereochemical Investigation of Palladium(II) Complexes with Phenanthroline Ligands: A Molecular Mechanics Approach

Abstract

Specific force field parameters have been derived through an optimisation procedure based on crystal structure data to describe the geometry of Pd II -phenanthroline complexes. The X-ray structure of [Pd(CH 3 )(3-sBu-phen) 2 ][OTf] is also reported. Molecular mechanics calculations show that intramolecular steric interactions yield severe distortions from a square-planar geometry of the metal atom, both in bischelated [Pd(3-R-phen) 2 ] 2+ and monochelated [Pd(CH 3 )(3-Rphen) 2 ] + complexes. A complete stereochemical analysis of the possible diastereoisomers of this last complex (R = sBu) allows the rationalisation of its fluxional behaviour observed

Single Isolated Pd2+ Cations Supported on N-Doped Carbon as Active Sites for Hydrogen Production from Formic Acid Decomposition

“…The formation of the Pd species attached to a pair of pyridinic nitrogen sites is also in line with the ability of palladium to form chelate complexes with N-containing organic ligands: for example, with phenanthroline containing a pair of pyridinic type nitrogen atoms. The structure of some complexes of Pd with this ligand is well studied. − These complexes were used as homogeneous catalysts for different reactions. Thus, recently it was shown that complexes of some noble metals and iron with phenanthroline type ligands are active in the conversion of CO 2 to formate species and in the dehydrogenation of formic acid .…”

“…The structure of some complexes of Pd with this ligand is well studied. [48][49][50] These complexes were used as homogeneous catalysts for different reactions. Thus, recently it was shown that complexes of some noble metals 51 and iron 52 with phenanthroline type ligands are active in conversion of CO 2 to formate species 51 and in dehydrogenation of formic acid.…”

Coordination-Directed Self-Assembly of M12L24 Nanocage: Effects of Kinetic Trapping on the Assembly Process

“…For the intermolecular and intramolecular interactions, a general AMBER force field was used in combination with CH and CH 2 united atom parameters from a reoptimized united atom force field . For Pd atoms, we used parameters from the literature . For the ligand atomic charges, we used restrained electrostatic potential (RESP) charges, obtained using ab initio molecular orbital calculations with the B3LYP/6-31G(d) level in the Gaussian03 program…”

“…34 For Pd atoms, we used parameters from the literature. 35 For the ligand atomic charges, we used restrained electrostatic potential (RESP) charges, 36 obtained using ab initio molecular orbital calculations with the B3LYP/6-31G(d) level in the Gaussian03 program. 37 Trajectories were produced using the MD program GRO-MACS (version 4.0.7) 38 with a modified nonbonded interaction routine to employ the WCA potential described above.…”

Synthesis and structural characterization of dicopper(II) and dipalladium(II) complexes of 1,1,2,2-tetrakis(carboxamido-2-methylpyridyl)ethane

“…Corresponding data for a PdAN(pyridyl) linkage does [20]. Since the CuAN(amido) bond stretch force constant (201.2 kcal/mol Å A For 2, a similar set of alterations in the optimized structure compared to the original crystal structure (Fig.…”