Inorganic Stereochemistry

1. Introduction.- A. Historical Background.- B. Theoretical Background.- 1. The Repulsion Law.- 2. Effective Bond Length Ratios.- 3. Repulsion Energy Coefficients.- 4. Multidentate Ligands.- 5. Trigonometry.- 2. Polyhedra.- A. Classic Geometric Polyhedra.- 1. Regular Polyhedra.- 2. Semiregular Polyhedra.- a) The Prisms.- b) The Antiprisms.- c) Thirteen Archimedean Polyhedra.- 3. Non-uniform Polyhedra.- a) Pyramids, Bipyramids, Capped Prisms, and Capped Antiprisms.- b) Cupolas and Bicupolas.- c) Diminished Icosahedra.- d) Five Unique Polyhedra.- B. Chemical Coordination Polyhedra.- 1. Distortions Arising from Different Sized Faces.- 2. Distortion of Non-spherical Polyhedra to Spherical Polyhedra.- 3. Some Additional Polyhedra.- 4. Distortion Resulting from Chelate Groups.- 5. Small Bond-length Distortions.- 3. Four-Coordinate Compounds.- A. Tetrahedral [M(unidentate A)(unidentate B)3].- 1. p-Block Elements Connected by Single Bonds.- 2. p-Block Elements Connected by Multiple Bonds.- 3. Compounds Containing a Non-Bonding Pair of Electrons.- 4. Atoms Bonded to Transition Metal Ions.- 5. Transition Metal Complexes.- B. Tetrahedral [M(unidentate A)2(unidentate B)2].- 1. p-Block Elements Connected by Single Bonds.- 2. p-Block Elements Connected by Multiple Bonds.- 3. Transition Metal Complexes.- C. A Comment on Square-Planar Complexes and the trans-Influence.- D. Tetrahedral [M(bidentate)(unidentate)2].- 4. Five-Coordinate Compounds Containing only Unidentate Ligands.- A. [M(unidentate)5].- B. [M(unidentate A)(unidentate B)4].- 1. Axially Substituted Trigonal Bipyramid, T1.- 2. Equatorially Substituted Trigonal Bipyramid, T0.- 3. Axially Substituted Square Pyramid, S2.- 4. [M(lone pair)(unidentate)4], Stereochemistry T0.- C. [M(unidentate A)2(unidentate B)3].- 1. Bi(Axially Substituted) Trigonal Bipyramid, T1.- 2. Bi(Equatorially Substituted) Trigonal Bipyramid, T0.- 3. Square Pyramid, S2.- 5. Five-Coordinate Compounds Containing Chelate Groups.- A. [M(bidentate) (unidentate)3].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- B. [M(bidentate)2 (unidentate)].- 1. The Theoretical Stereochemistries.- a) Symmetrical Structures.- b) Unsymmetrieal Structures.- 2. Comparison with Experiment.- C. [M(tridentate)(unidentate)2].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- 6. Six-Coordinate Compounds Containing only Unidentate Ligands.- A. [M(unidentate A)(unidentate B)5].- B. [M(unidentate A)2 (unidentate B)4].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- 3. Copper(II) Complexes.- C. [M(unidentate A)3(unidentate B)3].- 7. Six-Coordinate Compounds [M(Bidentate)2(Unidentate)2].- A. Relative Stability of cis- and trans-Octahedral Complexes.- B. Angular Distortions in cis-Octahedral Complexes.- C. Bond-length Distortions in cis-Octahedral Complexes.- D. Distortion of the trans-Octahedral Structure to the Skew-Trapezoidal Bipyramidal Structure.- E. Bis(dithiochelate) Complexes of Selenium (II) and Tellurium (II).- F. Unsymmetrical Bidentate Ligands.- G. Pentagonal Pyramidal [M(bidentate)2(unidentate A) (unidentate B)] Complexes.- 8. Six-Coordinate Compounds [M(Bidentate)3].- A. The Theoretical Stereochemistry.- B. Crystal Structures of 158 Complexes.- C. Distortions to Lower Symmetry.- D. Manganese (III) and Copper (II) Complexes.- E. Dithiolate Complexes.- F. Some Exceptional Structures.- G. Some Comments on Ligand Design.- H. Intramolecular Rearrangements.- I. Unsymmetrical Bidentate Ligands.- J. [M(bidentate A)(bidentate B)2].- 9. Six-Coordinate Compounds Containing Tridentate Ligands.- A. [M(tridentate)(unidentate)3].- B. [M(tridentate)2].- 10. Seven-Coordinate Compounds Containing only Unidentate Ligands.- A. Six Symmetrical Structures.- B. Relations Between the Pentagonal Bipyramid, Capped Octahedron, and Capped Trigonal Prism.- C. Comparison with Experiment.- D. [M(unidentate A)6(unidentate B)].- E. [M(unidentate)6(lone pair)].- F. [M(unidentate A)5(unidentate B)2].- G. [M(unidentate A)4(unidentate B)3].- 11. Seven-Coordinate Compounds Containing Chelate Groups.- A. [M(bidentate)(unidentate)5].- 1. Introduction.- 2. Stereochemistry A.- 3. Stereochemistries B and C.- 4. Stereochemistry D.- 5. Comparison with Experiment.- B. [M(bidentate)2(unidentate)3].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- C. [M(bidentate)3(unidentate)].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- 12. Eight-Coordinate Compounds Containing only Unidentate Ligands.- A. Seven Symmetrical Structures.- B. The Square Antiprism.- C. The Dodecahedron.- D. Relations Between the Square Antiprism, Dodecahedron, and Cube.- E. [M(unidentate A)4(unidentate B)4].- F. [M(unidentate A)2(unidentate B)6].- 13. Eight-Coordinate Compounds Containing Chelate Groups.- A. [M(bidentate)2(unidentate)4].- B. [M(bidentate)3(unidentate)2].- C. [M(bidentate)4].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- 3. Some Exceptional Structures.- 4. Further Comments on Ligand Design.- 14. Nine-Coordinate Compounds.- A. [M(unidentate)9].- B. [M(bidentate)3(unidentate)3].- C. [M(bidentate)4(unidentate)].- D. [M(tridentate)3].- 15. Ten-Coordinate Compounds.- A. [M(unidentate)10].- B. [M(bidentate)5].- 1. The Theoretical Stereochemistries.- 2. Comparison with Experiment.- 16. Twelve-Coordinate Compounds.- A. [M(unidentate)12].- B. [M(bidentate)6].- References.