title: Exact Ligand Solid Angles.
abstract: Steric demands of a ligand can be quantified by the area occluded by the ligand on the surface of an encompassing sphere centered at the metal atom. When viewed as solid spheres illuminated by the metal center, the ligand atoms generally cast a very complicated collective shadow onto the encompassing sphere, causing mathematical difficulties in computing the subtended solid angle. Herein, an exact, analytic solution to the ligand solid angle integration problem is presented based on a line integral around the multisegmented perimeter of the ligand shadow. The solution, which is valid for any ligand bound to any metal center, provides an excellent method for analyzing geometric structures from quantum chemical computations or X-ray crystallography. Over 275 structures of various metals bound to diverse mono- and multidentate ligands were optimized using B3LYP density functional theory to exhibit exact solid angle (Ω°) computations. Among the intriguing Ω° solutions, Pd(xantphos) and ferrocene exhibit holes in their ligand shadows, and Fe(EDTA)(2-) has a surprisingly simple shadow defined by only four arcs, despite having a multitude of overlaps among individual shadow cones.
authors.affiliation: Department of Chemistry and Center for Computational Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Jenna A
authors.initials: JA
authors.lastname: Bilbrey
authors.affiliation: Department of Chemistry and Center for Computational Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Arianna H
authors.initials: AH
authors.lastname: Kazez
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Jason
authors.initials: J
authors.lastname: Locklin
authors.affiliation: Department of Chemistry and Center for Computational Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Wesley D
authors.initials: WD
authors.lastname: Allen