The Impact of p-orbital on Optimization of ReH7(PMe3)2 Compound

AbstractThis study investigates the importance of the p-function used in the computational modeling. The geometric changes of ReH7(PMe3)2 system is used as the model compound. 6-31G, 6-311G and 6- 311++G basis sets were used for all elements except Re, which used Christiansen et. al. basis set. Upon removing the p-function on metal, we noticed the geometric changes are minimal as long as triple-zeta basis sets are used for rest of elements. While the relative energy profile of a reaction would still reasonably assemble each other, a direct comparison in energy between the basis set with and without p-function is not recommended

Systematic structural studies in metal complex chemistry

A procedure is presented for detecting geometrical preferences, deformations and interconversion pathways between different geometries for the transition metal coordination sphere ML(_n). A discrepancy index [R(_ang)(x)] was proposed initially to address the problems of dimensionality and permutation complexity in the systematic analysis of coordination sphere geometry with higher coordination numbers (n > 7). But it can also be used generally for the lower coordination numbers. A set of standard geometries for coordination numbers 2-9 are presented and the angles between the center point and each vertex for the polyhedra which are used to describe the coordination sphere geometries for coordination numbers 7-9 are idealised. These angles correspond to the metal-ligand valence angles in the coordination complex and are used as the standard values to measure the deviation of a real coordination sphere in the complex from these standard polyhedra. Geometry of each coordination sphere (ML(_7-9)) from the Cambridge Structural Database (CSD) is identified by the calculations of R(_ang)(x) values. Also the unique enumeration numbers of the ligands corresponding to each geometry can be derived over the n! ligand permutations. The different geometrical clusters and interconversion pathways from one to another are mapped in a designed two-dimensional plot. The symmetry coordinates and principal component analysis are initially applied in these higher coordination number systems. They not only map the clusters represented to those standard geometries in the different symmetric point groups but also provide and confirm the interconversion pathways between the different geometries. The other systematic study involves the analysis and correlation of the metal σ-π bond in the transition metal alkyne and alkene complexes from the CSD. Geometrical features of this specific bond are examined in the view of structure and some useful correlation between the key geometrical parameters are defined. Finally, X-ray crystal structure determinations are briefly described and the crystal structures of ten transition metal compounds in coordination numbers 4-6 are presented