کتاب شیمی معدنی پارسل – کاتز (purcell-katz)

مقدمه ای بر کتاب شیمی معدنی پارسل-کاتز (purcell-kotz)

دوستان کتاب شیمی معدنی پارسل کاتز یکی از بهترین کتاب های شیمی معدنی است که در دانشگاه های مختلف تدریس می شود. تیم کلینیک تخصصی علوم بنا به نیاز دانشحویان عزیز اقدام به اسکن تمامی صفحات کتاب پارسل کاتز کرده تا این کتاب را به علاقه مندان تقدیم کند . در ضمن پس از اسکن کتاب جهت راحتی شما ، تمامی صفحات کتاب شیمی معدنی پارسل کاتز  OCR شده تا قابل جستجو باشد.

فهرست مطالب کتاب پارسل – کاتز (purcell-kotz)

فهرست مطالب کتاب شیمی معدنی پارسل کاتز را در ادامه میبینیم.

1
USEFUL ATOMIC CONCEPTS • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 12
2
Probability Density Functions ………………………………. 13
The Electron as a Matter Wave. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Probability Density Functions …………………………… 17
Radial Density Functions and Orbital Energies …… . . . . . . . . . . . . 18
Angular Functions and Orbital Shapes . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Total Density Functions ……………………………….. 30
Polyelectronic Atoms ……………………………………… 33
Atom Electron Configurations and the Long Form Periodic Table. 33
Slater Orbitals and Their Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Atomic Configurations and Atomic Terms. . . . . . . . . . . . . . . . . . . . . . . 47
Atom and Orbital Electronegativities ……………………… 54
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Appendices to Chapter I …………………………………… 61
A. Hydrogen Type Wavefunctions
B. First Ionization Potentials of the Main Group and
Transition Elements
C. Electron Affinity Values of the Elements
BASIC CONCEPTS OF MOLECULAR TOPOLOGIES. . . . . . . . . . . . . . . . . . 64
Shared and Lone Pairs and Lewis Structures .. . . . . . . . . . . . . . . . . . . . . . . 65
Electron Pair Repulsion Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Symmetry Concepts ………………………………………. 82
Point Groups ………………………………………… 82
Character Tables … . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
..
VII
viii 0 CONTENTS
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Appendix to Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Point Group Character Tables
3
THE DIRECTED ATOMIC ORBITAL VIEW OF CHEMICAL BONDS • • • • • 98
Directional Atomic Orbitals ………………………………… 99
Molecular Properties Conveniently Interpreted with the Directed
Atomic Orbital Concept. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 107
Bond Distances ………………………………………. 108
Force Constants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 110
Dipole Moments ………………..…………………….. 114
Nuclear Spin Coupling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 117
Bond Energies ……………………………………….. 119
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 124
4
THE UNDIRECTED ORBITAL VIEW OF CHEMICAL BONDS. . . . . . .. . .. 126
5
Introductory Comments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 127
Molecular Orbital Probability Functions ………………………. 130
Principles of MO Construction and Interpretation… . . . . . . . . . . . . . . . . . .. 134
The Hydrogen Molecule ……………………………….. 134
Beryllium Hydride and Hydrogen Chloride. . . . . . . . . . . . . . . . . . . . .. 135
Summary ……………………………………………. 140
Main Group Diatomic Molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 141
Homonuclear Molecules ……………………………….. , 141
The pSU’, p7T Order Controversy …………………………. 145
Heteronuclear Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Structure, YSEPR, and LCAO-MO . . . . . . . . . . . . . . . . … . . . .. . . … … 149
The EF3 Series . ………… , ” ……………….. , . . . .. . . … 151
The EF4 Series . ……………….. ” …….. ” … . . . .. . . .. .. 153
“Linear” (One- Dimensional) Molecules ………………………. 155
Cyclic (Two- Dimensional) Molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 158
Polyhedral (Three- Dimensional) Molecules. . . . . . . . . . . . . . . . . . . . . . . . .. 163
Stratagem. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
EX 3 (D 311 ) • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •• 164
EX4 (Td)’ .. . . .. .. . . .. . . .. . . . . .. . . .. .. . . .. . . . . .. .. . . … . .. .. .. 169
EXs (D 3h ) … ” ………………………………………. , 171
EX4 (D 4h ) . . . .. . . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . . . . . .. . . .. . . . . .. 174
EXs (011) ……………………………………………. 177
The Equivalence of the Localized and Delocalized Models. . . . . . . . . . . . 183
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
THE DONOR/ACCEPTOR CONCEPT
• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 186
Introduction …………………………………………….. 186
Survey of Adduct Types …………………………………… 188
6
CONTENTS 0 ix
Acidic and Basic Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 188
Non-Metal Acids and Bases…………………………….. 194
Boron and Aluminum ……………………. . . . . . . . . . . .. 194
Carbon and Silicon ………………………………… 196
Nitrogen and Phosphorus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 203
Oxygen and Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 205
Halogens ………………………………………… 209
Xenon. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 212
Metals . ……………………………………. , . . . . . . . . .. 213
Acid-Base Strengths ….. . …………………………………. 216
The Thermodynamic Definition ……………… .. ……. . …. 216
Quantitative Prediction of Relative Adduct Stabilities ………… 218
Illustrative Interpretations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 225
Proton Affinities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 226
(CH3hN, (SiH3hN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 228
Picolines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 229
Et3N, HC(C2 H4hN … . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 229
Me3N’MMe3, M = B, AI, Ga, In ……………………. 229
1T Resonance Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 230
BF::::Me3– X ……………………………………….. 232
Retrodative Bonding ………………………………. , 232
An Acid-Base View of Solvation Phenomena. . . . . . . . . . . . . . . . . . . . . . .. 235
Liquid Ammonia ……………………………………… 241
Hydrofluoric and Sulfuric Acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 249
Sulfur Dioxide ……………………………………….. 255
HS03F and Superacids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 259
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 263
ENERGETICS AND STRUCTURES AS GUIDES TO MAIN
GROUP CHEMISTRY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 264
Free Energy, Reaction Potential, and Equilibrium. . . . . . . . . . . . . . . . . . .. 265
Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 265
Estimation of Reaction Spontaneity. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 266
The Non Sequitur” Stability” ……………………….. 267
Heats of Reactions from Bond Energies. . . . . . . . . . . . . . . . . . . .. 268
Higher Oxidation State Stabilization . . . . . . . . . . . . . . . . . . . . . . .. 271
A Caveat Concerning Condensed Phase Reactions. . . . . . . . . .. 274
Metal-Containing Solids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 276
Lattice Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 276
Structure and Stoichiometry …………………… . ………. 279
Structure and the Concept of Ion Radii …………. . . . . . . . . . . .. 283
Layer Lattices and Incipient Covalency. . . . . . . . . . . . . . . . . . . . . . . .. 286
Synthesis Principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 290
Cation Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 291
Ionic Fluorinating Agents …………………………… 292
Ion Size and Compound Isolation from Solution . . . . . . . . . . . .. 293
Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 296
Structures and Bonding …………………………….. 296
Oxidative Stabilities …………………………… ; …. 299
x 0 CONTENTS
Non-Metal Compounds • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Boron and Aluminum .. ……….. ………………….. …. .
Carbon and Silicon …………………………………… .
Nitrogen and Phosphorus ………………………………. .
Oxygen and Sulfur ……………………………………. .
Halogens …………………………………………… .
Noble Gases . .. ……………… …….. ……………… . .
Epilog .. ……………………………………………….. .
7
300
300
316
329
340
349
354
357
REACTION PATHWAYS • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 358
8
Basic Concepts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 359
Rate Expressions and Interpretations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 364
General Formulation…. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 364
Second Order Rate Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 366
Pseudo- First Order Rate Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 368
First Order Rate Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 369
Activation Parameters …………………………………….. 371
A Caveat Concerning Solvent Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 372
The Constraint of Orbital Following. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 373
The Principle of Microscopic Reversibility .. . . . . . . . . . . . . . . . . . . . . . . .. 378
Survey of Reactions ………………………………………. 382
One Valence Pair. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 383
Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 383
Three Valence Pairs …….. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 386
Boron …………………………………………… 386
Four Valence Pairs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 393
Boron …………………………………………… 393
Silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 40 I
Nitrogen and Phosphorus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 410
Oxygen and Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 422
Halogens ………………………………………… 429
Five Valence Pairs ……………………………………. 430
Phosphorus and Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430
Epilog . ……………………………………………….. ” 444
SYNTHESIS OF IMPORTANT CLASSES OF NON-METAL
COMPOUNDS …………………………………………….. 446
Special Techniques ……………………………………….. 447
The Chemical Vacuum Line. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 447
Plasmas …………………………………………….. 449
Photochemical Apparatus ………………………………. 450
Electrolysis …… . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 450
An Overview of Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 452
Synthesis of Fluorides and Chlorides …………………………. 453
Boron and Aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
Silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 457
.
Nitrogen and Phosphorus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 457
9
CONTENTS 0 xi
Oxygen and Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 459
Fluorine and Chlorine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 462
Xenon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 463
Fluorinating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 465
SbF3 and SbF5 …..•…..•••..• • …••….•…•….••…•….. 466
CIF, CIF3, BrF3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 467
Sulfur Tetrafluoride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 468
Dinitrogen Tetrafluoride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 470
ChioropentafluorosuIfu r …….. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 472
Chloride Substitution by Hydrogen and Organics … . ……………. 474
Organometal Reagents …………………………… . …… 475
Boron and Aluminum .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 476
Silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 477
Nitrogen and Phosphorus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 477
Oxygen and Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 479
Halogens ……………………………………………. 481
Hydrometalation and Others. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 483
Catenation by Coupling …………… . ……………………… 486
Solvolysis Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 488
Boron and Aluminum ………………………………….. 488
Silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 494
Nitrogen and Phosphorus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 496
Oxygen and Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 503
Halogens and Xenon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 511
Epilog ……………………. ·, ……. ‘. . …………………… 513
FUNDAMENTAL CONCEPTS FOR TRANSITION METAL
COMPLEXES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. . . . . .. . .. 514
A Sampler ………. . ……………. . ……………………… 515
The Language of Coordination Chemistry . . . . . . . . . . . . . . . . . . . . . . . 517
Spectral/Magnetic Characteristics of Transition Ion Complexes. . .. 520
Structure Puzzles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 525
The Transition Metals and Periodic Properties. . . . . . . . . . . . . . . . . . . . . .. 527
The Molecular Orbital Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 531
General View of M D6 and M D4 Structures …….. ; . . . . . . . . . . . .. 533
MD6 (0,,) . . . . . . . .. . . .. .. . . . . . . . . . . .. . . .. . . .. .. . . . . . . . . . .. 533
MD 4 (D 4h ) ……•…………..••………….. • ; …….. 537
MD4 (Td) . . . . . . . . . . . . .. . . . . . . . . . . .. . . . . .. . . . . . . . . . . . . . . .. 541
The Angular Overlap Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 543
Tenets. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 543
d* Orbital Energies and Occupation Numbers …………… 545
Complex Structures and Preferences. . . . . . . . . . . . . . . . . . . . . . .. 549
Experimental Evidence for a Structural Preference Energy
and the Ligand Field Stabilization Energy . . . . . . . . . . . . . . . . . . . .. 551
Jahn-Teller Distortions from 0 h Geometry . . . . . . . . . . . . . . . . . . . . .. 553
Electronic States and Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 559
Ground and Excited States ……………………………. .. 560
The Energies of Electronic Transitions. . . . . . . . . . . . . . . . . . . . . . . . .. 567
The Spectrochemical Series .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 575
Paramagnetism of Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 577
•
xii 0 CONTENTS
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 583
Appendix to Chapter 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 584
State Energy Diagrams for M D6 (0,,)
10
COORDINATION CHEMISTRY: STRUCTURAL ASPECTS. . . . . . .. . . .. .. 586
General Considerations ……………………………………. 587
Low Coordination Numbers ………………………………… 590
Two-Coordinate Complexes …………………………….. 590
Three-Coordinate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 591
Four-Coordinate Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 593
Tetrahedral Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 593
Square Planar Complexes …………………………… 594
Five-Coordinate Complexes …………………………….. 596
Six-Coordinate Complexes ……………………………… 600
Polyhedra of High Coordination Number ……………………… 603
Seven-Go.ordinate Complexes .. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 604
Eight-Coordinate Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 606
Complexes Having Coordination Numbers of Nine or Higher. . . .. 609
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 609
11
COORDINATION CHEMISTRY: ISOMERISM. .. .. . . .. . . . . . . . . . . .. . . … 610
•
Constitutional Isomerism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 613
Hydrate Isomerism …. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 613
Ionization Isomerism ………………………………….. 614
Coordination Isomerism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 614
Polymerization Isomerism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 614
Linkage Isomerism …. , ……………………. , ” …….. ” 615
Stereoi somerism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 619
General Aspects of Stereochemical Notation in Coordination
Chemistry …………………………………………. 622
Four-Coordinate Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 625
Six-Coordinate Complexes ……………………………… 628
Isomerism from Ligand Distribution and Unsymmetrical
Ligands; Isomer Enumeration. . . . . . . . . . . . . . . . . . . . . . . . . . .. 629
Isomerism from Ligand Conformation and Chirality. . . . . . . . .. 636
Chirality and the Special Nomenclature of Chiral
Coordination Complexes ……………………………… 638
Optical Activity, ORD, and CD …………………………. 644
Absolute Configurations of Chiral Coordination Complexes. . . . . .. 647
Ligand Conformation ………………………………….. 650
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 653
12
COORDINATION CHEMISTRY: REACTION MECHANISMS AND
METHODS OF SYNTHESIS; ELECTRON TRANSFER REACTIONS. . . .. 654
•
Mechanisms of Electron Transfer Reactions. . . . . . . . . . . . . . . . . . . . . . . .. 659
CONTENTS 0 xiii
Key Ideas Concerning Electron Transfer Between
Transition Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 660
Outer Sphere Electron Transfer Reactions …………………. 660
Chemical Activation and Electron Transfer. . . . . . . . . . . . . . . . .. 662
Cross Reactions and Thermodynamics. . . . . . . . . . . . . . . . . . . . .. 667
Inner Sphere Electron Transfer Reactions. . . . . . . . . . . . . . . . . . . . . .. 669
Formation of Precursor Complexes. . . . . . . . . . . . . . . . . . . . . . . .. 671
Rearrangement of the Precursor Complex and Electron
Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 673
Electronic Structure of the Oxidant and Reductant. . . . . . . . . .. 673
The Nature of the Bridge Ligand. . . . . . . . . . . . . . . . . . . . . . . . . .. 675
Fission of the Successor Complex. . . . . . . . . . . . . . . . . . . . . . . . .. 679
Two-Electron Transfers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 680
Non-Complementary Reactions … . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 681
Synthesis of Coordination Compounds Using Electron
Transfer Reactions ……………………………………… 684
Epilog ……… ………………………………………… ” 693
13
COORDINATION CHEMISTRY: REACTION MECHANISMS AND
METHODS OF SYNTHESIS; SUBSTITUTION REACTIONS. . . . . . . . . . . .. 694
Replacement Reactions at Four-Coordinate Planar Reaction
Centers ……… ……………………….. : . . . . . . . . . . . . . . . .. 696
The General Mechanism of Square Planar Substitution
Reactions …. …………………………………….. ” 697
Factors Affecting the Reactivity of Square Planar
Complexes of Pt(II) and Other d 8 Metal Ions. . . . . . . . . . . . . . . . .. 700
lnfluence of the Entering Group. . . . . . . . . . . . . . . . . . . . . . . . . . .. 700
Influence of Other Groups in the Complex Ligands
trans to the Entering Group ……………………….. 702
Influence of Other Groups in the Complex-Ligands
cis to the Entering Group …………………………. 707
The Nature of the Leaving Group. . . . . . . . . . . . . . . . . . . . . . . . .. 707
Effect of the Central Metal … . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 708
The Intimate Mechanism for Replacement at Four-Coordinate
Planar Reaction Centers …………………………….. ” 708
Substitution Reactions of Octahedral Complexes. . . . . . . . . . . . . . . . . . . .. 710
Replacement of Coordinated Water ………………….‘….. ” 713
The Mechanism of Water Replacement ………………… 713
Rates of Water Replacement ……………………….. ” 716
Orbital Occupation Effects on Substitution Reactions
of Octahedral Complexes ………………………… ” 719
Solvolysis or Hydrolysis …………………………………. 721
Hydrolysis under Acidic Conditions. . . . . . . . . . . . . . . . . . . . . . .. 721
Base-Catalyzed Hydrolysis: The Conjugate Base or
CB Mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . .. 725
Synthesis of Coordination Compounds by Substitution
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 731
Thermodynamic Stability of Coordination Compounds. . . . . . . . . . .. 733
The Synthesis and Chemistry of Some Cobalt Compounds. . . . . . .. 742
The Synthesis and Chemistry of Some Platinum Compounds. . . . .. 750
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 755
•
xiv 0 CONTENTS
14
COORDINATION CHEMISTRY: REACTION MECHANISMS AND
METHODS OF SYNTHESIS; MOLECULAR REARRANGEMENTS
AND REACTIONS OF COORDINATED LIGANDS.. . . . . . . . . . . . . . . . . . . .. 756
Molecular Rearrangement s …………………………… .. ….. 757
Four-Coordinate Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 757
Six-Coordinate Octahedral Complexes. . . . . . . . . . . . . . . . . . . . . . . . .. 764
Reactions at Coordinated Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 773
Reactions Due to Metal Ion Polarization of Coordinated
Ligands ……………………………………………. 774
Hydrolysis of Amino Acid Esters and Amides and
of Peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 774
Aldol Condensation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 78 1
Imine Formation, Hydrolysis, and Substituent Exchange ….. 782
The Template Effect and Macrocyclic Ligands ……………… 783
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 790
15
FROM CLASSICAL TO ORGANOMETALLIC TRANSITION
METAL COMPLEXES AND THE SIXTEEN AND EIGHTEEN
ELECTRON RULE …………………………………………. , 792
The Sixteen and Eighteen Electron Rule …. . . . . . . . . . . . . . . . . . . . . . . .. 793
Theoretical Aspects of the 16 and 18 Electron Rule ……………… 804
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 807
16
ORGANOMETALLIC CHEMISTRY: SYNTHESIS, STRUCTURE,
AND BONDING …………………………………… ,……… 810
Introduction …………………………………………….. 811
A Note on the Organization of Organometallic Chemistry ………… 815
The Literature of Organometallic Chemistry …………………… , 816
Carbon (J’ Donors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 817
The Synthesis of Metal Alkyls and Aryls ………………….. 817
Direct Reaction of a Metal with an Organic Halide ………. 818
Thermod ynamic Considerations . . . . . . . . . . . . . . . . . . . . . . .. 818
Experimental Considerations …………………….. , 820
Reactions of Anionic Alkylating Agents with Metal
Halides or Oxides ……………………………….. 824
Reaction of a Metal with a Mercury Alkyl or Aryl . . . . . . . . . .. 825
Metalation Reactions: Metal-Hydrogen Exchange. . . . . . . . . . .. 826
Oxidative Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 829
Reactions of Metal-Containing Anions with Organic
Halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 830
I ,2-Addition of Metal Complexes to Unsaturated
Substrates ……………………………………… 832
Hydrometalations …………………………. . …. , 832
Oxymetalations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
Halometalations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 838
CONTENTS CJ xv
Organometalations ……………………… : . . . . . . .. 839
Structure and Bonding in Metal Alkyls and Aryls …… . . . . . . . . .. 843
Metal Carbonyls. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 855
The Synthesis of Metal Carbonyls . . . . . . . . . . . . . . . . . . . . . . . . .. 856
Metal Carbonyls: Properties and Structures …………….. 858
Bonding in Metal Carbonyls …………………………. 861
Metal-Carbene and -Carbyne Complexes. . . . . . . . . . . . . . . . . . . . . . .. 863
Carbon 1r Donors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 866
Chain 1r Donor Ligands (Olefins, Acetylenes. and 1r-Allyl) . . . . . . .. 867
Synthesis of Olefin. Acetylene. and 1r- All yl Complexes. . . . . .. 868
Olefin Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 868
Acetylene Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 870
1r-Allyl Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 871
Structure and Bonding in Olefin. Acetylene, and
1r-Allyl Complexes……………………………….. 871
Complexes with Cyclic 1r Donors ………………………… 876
Synthesis and Properties ……………………………. 877
Structure and Bonding ……………………………… 883
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 898
Appendix to Chapter 16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 899
Metal Carbonyls and Infrared Spectroscopy
17
ORGANOMETALLIC COMPOUNDS: REACTION PATHWAYS • • • • • • • • • • 906
The 16 and 18 Electron Rule and Reactions of Transition
Metal Organometallic Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 909
Association Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 910
The Lewis Acidity and Basicity of Organometallic
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 910
Ligand Protonation ……………………………………. 916
Substitution Reactions …………………………………….. 918
Nucleophilic Ligand Substitutions. . . . .. . . . . . . .. . . .. . . . . .. . . . . .. 918
Electrophilic and Nucleophilic Attack on Coordinated Ligands . . .. 923
Addition and Elimination Reactions ……….. : ……………….. 927
1,2- Additions to Double Bonds ………………………….. 927
1, I-Addition to CO: Carbonylation and Decarbonylation ……… 933
Oxidative Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 938
General Considerations …………………………….. 939
Stereochemistry of Oxidative Additions. . . . . . . . . . . . . . . . . . . .. 941
Influence of Central Metal, Ligands, and Addend on
Oxidative Addition ………………………………. 943
Mechanism of Oxidative Addition. . . . . . . . . . . . . . . . . . . . . . . . .. 947
Elimination Reactions and the Stability of Metal-Carbon
a Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 948
Rearrangement Reactions ………………………………….. 953
Redistribution Reactions ……………………………….. 953
Fluxional Isomerism or Stereochemical Non- Rigidity. . . . . . . . . . . .. 957
Catalysis Involving Organometallic Compounds ………………… 962
Olefin Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 963
The Oxo Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 966
xvi D CONTENTS
The Wacker Process (Smidt Reaction) . . . . . . . . . . . . . . . . . . . . . . . . .. 967
Polymerization ……………………………………….. 970
Cyclooligomerization, Olefin Isomerization and Metathesis,
and Polymer-Bound Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 976
Epilog. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 979
18
MOLECULAR POLYHEDRA: BORON HYDRIDES AND METAL
CLUSTERS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 980
The Boron Hydrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 983
The Neutral Boron Hydrides , (BH)pHq . …………………… 988
Structure and Bonding ……………………………… 988
The Topological Approach to Boron Hydride
Structure: the styx Numbers. . . . . . . . . . . . . . . . . . . . . . . .. 990
Molecular Orbital Concepts ……………………… 994
Synthesis and Reactivity of the Neutral Boron
Hydrides …………………… . .. . ……………… 997
A General Organizational Scheme for the Neutral Boron
Hydrides , the Closo Polyhedral Hydroborate Ions, and
the Carboranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1005
A Molecular Orbital View of Closo-Hydroborate Anions
and Carboranes …………………………………….. 1009
Closo- Hydroborate Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1011
The Carboranes ……. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1015
Metallocarboranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1020
Metal-Metal Bonds and Metal Clusters ……………………….. 1026
Binuclear Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1027
Three- Atom Clusters ………………… . ………………. 1033
Four-Atom , Tetrahedral Clusters ….. . ……………………. 1035
Five- and Six- Atom Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1040
Epilog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1045
Appendix to Chapter 18 ………………………………….. ” 1047
Bonding Model for M6 Clusters
19
BIOCHEMICAL APPLICATIONS • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 1050
The Cell …………. . ……………………………………. 1051
Processes Coupled to Phosphate Hydrolysis. . . . . . . . . . . . . . . . . . . . . . . .. 1053
Nucleotide Transfer- DNA Polymerase . . . . . . . . . . . . . . . . . . . . . . .. 1055
Phosphate Transfer ……………………………………. 1057
General Comments ………. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1058
Pyruvate Kinase …… . …………………………….. 1058
Glucose Storage- Phosphoglucomutase. . . . . . . . . . . . . . . . . . . .. 1060
Phosphate Storage in Muscle Creatine Kinase ………….. 1061
Na+/K+ Ion Pump ATPase ………………………… 1063
Oxygen Carriers Hemoglobin and Myoglobin …………………. 1064
Cobalamins; Vitamin B12 Coenzyme ………………………….. 1073
CONTENTS 0 xvii
Electron Transfer Agents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1078
Cytochromes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1078
Iron-Sulfur Proteins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1082
I-Fe-S and 2-Fe So ……………………………… 1082
2-Fe-S* ……………………. ……. …. .. ………. 1083
8-Fe-S* …………………………………………. 1084
N 2 Fixation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1086
Chlorophyll ……………………….. . . . . . . . . . . . . . . . . . . . .. 1090
Epilog . ………………………………….. , ……………. 1095
COMPOUND INDEX ………………………………………… 1097
SUBJECT INDEX …………………………………………… 1105

مشخصات فایل دانلودی کتاب پارسل کاتز»

نوع فایل : پی دی اف

تعداد صفحات : 1134

کیفیت : اسکن با کیفییت بسیار بالا

حجم فایل : 657 مگابایت