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Exact Ligand Solid Angles
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DOI：10.1021/ct400426e.png)
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Abstract
En 中文
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 (Omega degrees) computations. Among the intriguing Omega degrees 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.
Keywords:
CONFORMATIONALLY FLEXIBLE LIGANDS
MOLECULAR MECHANICS MODEL
RAY STRUCTURAL DATA
BITE ANGLE
ORGANOMETALLIC CHEMISTRY
X-RAY
HOMOGENEOUS CATALYSIS
DIPHOSPHINE LIGANDS
PHOSPHORUS LIGANDS
BIDENTATE LIGANDS
Journal
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5.5
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5.4W