Inorganic Stereochemistry

ISBN-13: 9783642680489 / Angielski / Miękka / 2011 / 230 str.

D. L. Kepert

Opis

Molecular stereochemistry is a fundamental aspect of all areas of chemistry. It is especially important in inorganic chemistry where the coordination numbers are variable and occasionally quite high. The present book evolved naturally from a series of articles written by Professor Kepert for Progre88 in Inorganic Ohemi8try, elucida ting aspects of the stereochemistry of inorganic compounds of co ordination numbers 4-12. In the present volume, Professor Kepert has added new sections and synthesized these individual chapters into a unified treatment, updating his references when necessary to the most recent contributions in the literature, and inter weaving the various themes as deemed appropriate. The result is a major contribution, describing the stereochemistry of coordi nation compounds having both unidentate and multidentate ligands. The viability of the repulsion approach to stereochemistry is tested to the limit in this treatise and shown to be an extremely good way of rationalizing a diverse body of data."

Spis treści

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.