Chemical Synthesis Using Highly Reactive Metals

1 - Title Page [Seite 5]
2 - Copyright Page [Seite 6]
3 - Contents [Seite 7]
4 - Preface [Seite 19]
5 - Chapter 1 Genesis of Highly Reactive Metals [Seite 21]
6 - Chapter 2 General Methods of Preparation and Properties [Seite 25]
6.1 - 2.1 General Methods for Preparation of Highly Reactive Metals [Seite 25]
6.2 - 2.2 Physical Characteristics of Highly Reactive Metal Powders [Seite 28]
6.3 - 2.3 Origin of the Metals' High Reactivity [Seite 29]
6.4 - References [Seite 30]
7 - Chapter 3 Zinc [Seite 33]
7.1 - 3.1 General Methods for Preparation of Rieke Zinc [Seite 33]
7.2 - 3.2 Direct Oxidative Addition of Reactive Zinc to Functionalized Alkyl, Aryl, and Vinyl Halides [Seite 36]
7.2.1 - Typical Preparation of 3-Fluorobenzylzinc Bromide [Seite 39]
7.2.2 - Typical Preparation of 4-Cyanobutylzinc Bromide [Seite 40]
7.2.3 - Typical Preparation of 4-Bromophenylzinc Iodide [Seite 40]
7.2.4 - Typical Preparation of 3-Methyl-2-Pyridlyzinc Bromide [Seite 40]
7.3 - 3.3 Reactions of Organozinc Reagents with Acid Chlorides [Seite 40]
7.3.1 - Typical Generation of Organozinc Halides from Organic Halides and Active Zinc and Their Copper-Mediated Coupling with Acid Chlorides [Seite 41]
7.3.2 - Synthesis of 4-Methoxy-2?-Thiomethylbenzophenone Using Tetrakis(triphenylphosphine)palladium(0) as Catalyst [Seite 46]
7.3.3 - Synthesis of Ethyl 7-(3,4-Difluorophenyl)-7-Oxoheptanoate Using Copper Iodide as Catalyst [Seite 46]
7.3.4 - Cyanide-Based Rieke Zinc [Seite 47]
7.4 - 3.4 Reactions of Organozinc Reagents with ?,??Unsaturated Ketones [Seite 47]
7.4.1 - Typical Copper-Mediated Conjugate Addition Reaction of Organozinc Halides to ?,?-Unsaturated Ketones [Seite 50]
7.5 - 3.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides [Seite 50]
7.5.1 - Typical Reaction of Organozinc Halides with Allylic Halides [Seite 51]
7.5.2 - Preparation of 2,3-Di(p-Cyanobenzyl)-1,3-Butadiene Reaction [Seite 54]
7.6 - 3.6 Negishi Cross-Coupling of Vinyl and Aryl Organozinc Halides [Seite 54]
7.6.1 - Typical Procedure for the Reaction of RZnX with Aryl and Vinyl Halides [Seite 56]
7.6.2 - Preparation of Aryl Ketones via Ni-Catalyzed Negishi Coupling Reactions [Seite 56]
7.6.3 - Typical Reaction Procedure [Seite 62]
7.7 - 3.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc [Seite 62]
7.8 - 3.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides [Seite 64]
7.9 - 3.9 Electrophilic Amination of Organozinc Halides [Seite 70]
7.10 - 3.10 Reformatsky and Reformatsky-Like Reagents and Their Chemistry [Seite 72]
7.10.1 - Synthesis of Reformatsky Reagent in THF [Seite 73]
7.10.2 - Synthesis of Reformatsky Reagent in Diethyl Ether [Seite 73]
7.11 - 3.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions [Seite 74]
7.12 - 3.12 Preparation of Tertiary Amides via Aryl, Heteroaryl, and Benzyl Organozinc Reagents [Seite 75]
7.13 - 3.13 Preparation of 5-Substituted-2-Furaldehydes [Seite 81]
7.13.1 - Results and Discussion [Seite 83]
7.13.2 - General Procedure for Pd-Catalyzed Cross-Coupling Reactions [Seite 93]
7.14 - 3.14 Preparation and Chemistry of 4-Coumarylzinc Bromide [Seite 93]
7.15 - 3.15 Preparation and Cross-Coupling of 2-Pyridyl and 3-Pyridylzinc Bromides [Seite 97]
7.15.1 - Results and Discussion [Seite 100]
7.15.1.1 - Conclusions [Seite 122]
7.15.1.2 - Experimental [Seite 123]
7.15.1.2.1 - General [Seite 123]
7.15.1.2.2 - Preparation of 2-Pyridylzinc Bromide (P1) [Seite 123]
7.15.1.2.3 - Preparation of 3-Pyridylzinc Bromide (P7) [Seite 123]
7.15.1.2.4 - General Procedure for Copper-Free Coupling Reactions [Seite 124]
7.15.1.2.5 - Pd-Catalyzed Coupling Reaction with 4-Iodoanisole (10b) [Seite 124]
7.15.1.2.6 - Preparation of Bipyridines [Seite 124]
7.15.1.2.7 - Pd-Catalyzed Coupling Reaction with Haloanilines [Seite 124]
7.15.1.2.8 - Pd-Catalyzed Coupling Reactions with Halophenols [Seite 125]
7.15.1.2.9 - Copper-Catalyzed SN2 Addition Reactions [Seite 125]
7.15.1.2.10 - Pd-Catalyzed Bimolecular Coupling Reactions [Seite 125]
7.15.1.2.11 - Preparation of Quinolinylzinc Reagents and Subsequent Coupling Reactions [Seite 125]
7.16 - 3.16 Preparation of Functionalized ?-Chloromethyl Ketones [Seite 126]
7.17 - 3.17 Rieke Zinc as a Reducing Agent for Common Organic Functional Groups [Seite 128]
7.17.1 - The General Procedure for Dissolving Zinc Metal Reduction [Seite 131]
7.18 - 3.18 Detailed Studies on the Mechanism of Organic Halide Oxidative Addition at a Zinc Metal Surface [Seite 131]
7.18.1 - Results and Discussion [Seite 132]
7.18.1.1 - Competitive Kinetics [Seite 132]
7.18.1.2 - Alkyl Bromides [Seite 134]
7.18.1.3 - Aryl, Vinyl, Benzyl, and Allyl Bromides [Seite 134]
7.18.1.4 - Stereochemical Studies [Seite 137]
7.18.1.5 - Radical Detection [Seite 139]
7.18.1.6 - Mechanistic Considerations [Seite 140]
7.18.1.7 - Two-Electron Mechanisms: SN2 [Seite 141]
7.18.1.8 - Ate Complex [Seite 141]
7.18.1.9 - SN1 [Seite 141]
7.18.1.10 - One-Electron Mechanisms [Seite 142]
7.18.1.11 - Outer-Sphere Electron Transfer [Seite 142]
7.18.1.12 - Inner-Sphere Electron Transfer [Seite 142]
7.18.1.13 - Linear-Free Energy Relationships (LFERs) [Seite 145]
7.18.1.14 - Synthetic Applications [Seite 149]
7.18.1.15 - Conclusions [Seite 150]
7.19 - 3.19 Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc: A New Class of Plastic Semiconductors [Seite 153]
7.19.1 - Results and Discussion [Seite 156]
7.19.1.1 - Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc [Seite 156]
7.19.1.2 - Mechanistic Implications of the Polymerizations [Seite 157]
7.19.2 - Spectroscopic Studies and Other Characterization [Seite 159]
7.19.2.1 - NMR Spectroscopy [Seite 159]
7.19.2.2 - Conclusion [Seite 163]
7.19.2.3 - General Preparation of Regioregular HT Poly(3-Alkylthiophenes) from 2,5-Dibromo-3-Alkylthiophenes: Preparation of Regioregular HT Poly(3-Hexylthiophene) (4b) [Seite 163]
7.19.2.4 - General Preparation of Regiorandom Poly(3-Alkylthiophenes) from 2,5-Dibromo-3-Alkylthiophenes: Preparation of Regiorandom Poly(3-Hexylthiophene) (5b) [Seite 164]
7.20 - References [Seite 164]
8 - Chapter 4 Magnesium [Seite 181]
8.1 - 4.1 General Background and Mechanistic Details of Grignard Reaction [Seite 181]
8.1.1 - General Methods of Metal Activation [Seite 184]
8.2 - 4.2 General Methods for Preparation of Rieke Magnesium [Seite 185]
8.3 - 4.3 Grignard Reagent Formation and Range of Reactivity of Magnesium [Seite 187]
8.4 - 4.4 1,3-Diene-Magnesium Complexes and Their Chemistry [Seite 192]
8.4.1 - Cyclizations of (1,4-Diphenyl-2-butene-1,4-diyl)magnesium with ?,?-Alkylene Dihalides [Seite 193]
8.5 - 4.5 Regioselectivity of Reaction of Complexes with Electrophiles [Seite 193]
8.6 - 4.6 Carbocyclization of (1,4-Diphenyl-2-butene-1,4-diyl) magnesium with Organic Dihalides [Seite 195]
8.7 - 4.7 1,2-Dimethylenecycloalkane-Magnesium Reagents [Seite 195]
8.8 - 4.8 Synthesis of Fused Carbocycles, ?-?-Unsaturated Ketones, and 3-Cyclopentenols from Conjugated Diene-Magnesium Reagents [Seite 198]
8.9 - 4.9 Synthesis of Spiro-?-Lactones and Spiro-?-Lactones from 1,3-Diene-Magnesium Reagents [Seite 204]
8.10 - 4.10 Synthesis of ?-Lactams from Conjugated Diene?Magnesium Reagents [Seite 210]
8.11 - 4.11 Low-Temperature Grignard Chemistry [Seite 212]
8.11.1 - Results and Discussion [Seite 214]
8.11.1.1 - Typical Procedure for the Preparation of the Corresponding Grignard Reagents [Seite 216]
8.12 - 4.12 Typical Procedures for Preparation of Active Magnesium and Typical Grignard Reactions as Well as 1,3-Diene Chemistry [Seite 217]
8.12.1 - Anhydrous Magnesium Salts [Seite 217]
8.12.2 - Preparation of Rieke Magnesium Using Potassium or Sodium as Reducing Agent [Seite 217]
8.12.3 - Preparation of a Grignard Reagent Using Rieke Magnesium Prepared Using Potassium-Potassium Iodide: 1-Norbornanecarboxyl Acid [Seite 219]
8.12.4 - Preparation of Rieke Magnesium Using Lithium and Naphthalene as an Electron Carrier [Seite 219]
8.12.5 - Chemistry of (2-Butene-1,4-diyl)magnesium: Preparation of Activated Magnesium (Mg*) [Seite 220]
8.12.6 - Typical Cyclization of (1,4-Diphenyl-2-butene-1,4-diyl)magnesium [Seite 220]
8.12.7 - Typical Reaction of (2,3-Dimethyl-2-butene-1,4-diyl)magnesium [Seite 221]
8.12.8 - Typical Stepwise Reaction of (2,3-Dimethyl-2-butene-1,4-diyl)magnesium [Seite 221]
8.12.9 - Typical Regioselective Reaction of Unsymmetrical (2-Butene-1,4-diyl)magnesium [Seite 222]
8.12.10 - Typical Reaction of Unsymmetrical (2-Butene-1,4-diyl)magnesium with SiCl4 [Seite 222]
8.12.11 - Typical Reaction with 1,2-Dimethylenecyclohexane [Seite 222]
8.13 - References [Seite 223]
9 - Chapter 5 Copper [Seite 229]
9.1 - 5.1 Background of Copper and Organocopper Chemistry [Seite 229]
9.2 - 5.2 Development of Rieke Copper [Seite 230]
9.3 - 5.3 Phosphine-Based Copper [Seite 231]
9.4 - 5.4 Lithium 2-Thienylcyanocuprate-Based Copper [Seite 240]
9.5 - 5.5 Copper Cyanide-Based Active Copper [Seite 244]
9.6 - 5.6 Formal Copper Anion Preparation and Resulting Chemistry [Seite 248]
9.7 - 5.7 Typical Experimental Details of Copper Chemistry [Seite 252]
9.7.1 - Active Copper from CuI and K [Seite 252]
9.7.2 - Reaction of K-Generated Copper with Pentafluorophenyl Iodide [Seite 253]
9.7.3 - Preparation of Phosphine-Based Copper [Seite 254]
9.7.4 - Phosphine-Based Copper Chemistry [Seite 254]
9.7.4.1 - Typical Reaction with Acid Chlorides to Form Ketones [Seite 254]
9.7.4.2 - Typical 1,4-Addition Reaction with 2-Cyclohexene-1-One [Seite 255]
9.7.4.3 - Typical Procedure for Intermolecular Epoxide-Opening Reaction [Seite 255]
9.7.4.4 - Typical Procedure for Intramolecular Epoxide-Opening Reaction [Seite 256]
9.7.5 - Lithium 2-Thienylcyanocuprate-Based Copper and Chemistry [Seite 256]
9.7.5.1 - Preparation of Thienyl-Based Activated Copper [Seite 256]
9.7.5.2 - Reaction of Organocopper Reagent with Acid Chlorides [Seite 257]
9.7.5.3 - Epoxide Opening of Organocopper Reagent with 1,2-Epoxybutane [Seite 257]
9.7.6 - Copper Cyanide-Based Active Copper and Chemistry [Seite 257]
9.7.6.1 - Preparation of Active Copper and Reaction with Organic Halides to Yield Organocopper Reagents [Seite 257]
9.7.6.2 - Cross-Coupling of Benzoyl Chloride with Organocopper Reagents Derived from CuCN?2LiBr-Based Active Copper [Seite 257]
9.7.6.3 - Conjugate Additions with Organocopper Reagents Derived from CuCN?2LiBr-Based Active Copper [Seite 258]
9.7.6.4 - Reaction of Allyl Organocopper Reagents Derived from CuCN?2LiBr with Benzoyl Chloride [Seite 258]
9.7.7 - Preparation of Copper Anions and Some Resulting Chemistry [Seite 258]
9.7.7.1 - Preparation of Cu(?1)Li(+) [Seite 258]
9.8 - References [Seite 259]
10 - Chapter 6 Indium [Seite 261]
10.1 - 6.1 Background and Synthesis of Rieke Indium [Seite 261]
10.2 - 6.2 Preparation of Organoindium Compounds [Seite 261]
10.2.1 - The Direct Synthesis of Diphenylindium Iodide and Ditolyindium Iodide from Activated Indium and Aryl Iodides [Seite 263]
10.3 - Results and Discussion [Seite 264]
10.4 - 6.3 Preparation and Reactions of Indium Reformatsky Reagents [Seite 266]
10.5 - 6.4 Experimental Details for Preparation and Reactions of Activated Indium [Seite 270]
10.5.1 - Preparation of Active Indium and Reaction with Alkyl Iodides [Seite 270]
10.5.2 - Reaction of Active Indium with Iodine [Seite 270]
10.5.3 - Triphenylindium [Seite 271]
10.5.4 - Tritolylindium [Seite 271]
10.5.5 - Trimethylindium [Seite 271]
10.5.6 - The Reaction of Activated Indium with Iodobenzene [Seite 272]
10.5.7 - The Reaction of Activated Indium with Iodotoluene [Seite 272]
10.5.8 - The Reaction of Triphenylindium with Iodine [Seite 272]
10.5.9 - Materials [Seite 272]
10.5.10 - Indium Reformatsky Reaction [Seite 273]
10.6 - References [Seite 273]
11 - Chapter 7 Nickel [Seite 275]
11.1 - 7.1 Preparation of Rieke Nickel, Characterization of Active Nickel Powder, and Some Chemistry [Seite 275]
11.1.1 - Preparation of Rieke Nickel Slurries [Seite 275]
11.1.2 - Surface Analysis [Seite 276]
11.1.3 - Discussion [Seite 277]
11.1.4 - Reactions of Slurries [Seite 278]
11.1.5 - Summary [Seite 279]
11.1.6 - Experimental Procedures [Seite 279]
11.1.6.1 - Preparation of a Typical Nickel Slurry [Seite 279]
11.1.6.2 - Preparation of Ni(C6F5)2[P(C2H5)3]2 [Seite 280]
11.1.6.3 - Preparation of Ni(C6F5)2(C5H5N)2 [Seite 280]
11.1.6.4 - Preparation of Ni(C6F5)2[(C6H5)2 PH]2?C6H5CH3 [Seite 280]
11.2 - 7.2 Preparation of 3-Aryl-2-hydroxy-1-propane by Nickel-Mediated Addition of Benzylic Halides to 1,2-Diketones [Seite 281]
11.2.1 - 2-Hydroxy-1,2,3-triphenyl-1-propanone (4a: Ar?=?R1?=?R2?=?C6H5): Typical Procedure [Seite 285]
11.3 - 7.3 Preparation of 3-Arylpropanenitriles by Nickel-Mediated Reaction of Benzylic Halides with Haloacetonitriles [Seite 285]
11.3.1 - Preparation of Metallic Nickel [Seite 286]
11.3.2 - Typical Procedure for 3-Phenylpropanenitrile (3a) [Seite 287]
11.4 - 7.4 Reformatsky-Type Additions of Haloacetonitriles to Aldehydes Mediated by Metallic Nickel [Seite 287]
11.5 - 7.5 Preparation of Symmetrical 1,3-Diarylpropan-2-ones from Benzylic Halides and Alkyl Oxalyl Chlorides [Seite 289]
11.6 - 7.6 Nickel-Mediated Coupling of Benzylic Halides and Acyl Halides to Yield Benzyl Ketones [Seite 293]
11.7 - 7.7 Nickel-Assisted Room Temperature Generation and Diels-Alder Chemistry of o-Xylylene Intermediates [Seite 295]
11.7.1 - Results and Discussion [Seite 297]
11.7.2 - Typical Preparation of Activated Nickel [Seite 302]
11.7.3 - Reaction of ?,??-Dibromo-o-xylene with Diethyl Fumarate in the Presence of Metallic Nickel [Seite 304]
11.8 - 7.8 Active Nickel-Mediated Dehalogenative Coupling of Aryl and Benzylic Halides [Seite 304]
11.8.1 - Results and Discussion [Seite 305]
11.8.2 - Results and Discussion [Seite 309]
11.8.3 - Preparation of Activated Nickel Powder [Seite 315]
11.8.4 - Reaction of 4-Iodomethoxybenzene with Activated Nickel Powder [Seite 316]
11.8.5 - Trapping of Bis(pentafluorophenyl)nickel(II) Species with Triphenylphosphine [Seite 316]
11.8.6 - Trapping of (Pentafluorophenyl)nickel(II) Iodide Species with Triethylphosphine [Seite 317]
11.8.7 - Preparation of Metallic Nickel Powders and Their Reaction with 4-Nitrobenzyl Chloride [Seite 317]
11.9 - References [Seite 318]
12 - Chapter 8 Manganese [Seite 325]
12.1 - 8.1 Preparation of Rieke Manganese [Seite 325]
12.2 - 8.2 Direct Formation of Aryl-, Alkyl-, and Vinylmanganese Halides via Oxidative Addition of the Active Metal to the Corresponding Halide [Seite 326]
12.3 - 8.3 Direct Formation of Organomanganese Tosylates and Mesylates and Some Cross-Coupling Reactions [Seite 336]
12.4 - 8.4 Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in New Reactions [Seite 340]
12.4.1 - Introduction [Seite 340]
12.4.2 - Results and Discussion [Seite 341]
12.4.2.1 - Preparation and Coupling Reactions of Benzylic Manganese Halides [Seite 341]
12.4.2.2 - Preparation and Coupling Reactions of Benzylic Manganese Sulfonates and Phosphates [Seite 342]
12.4.2.3 - Homocoupling Reactions of Functionalized Benzylic Manganese Reagents [Seite 352]
12.4.2.4 - Palladium-Catalyzed Cross-Coupling Reactions of Benzylic Manganese Reagents [Seite 355]
12.4.2.5 - Limitations of This Approach [Seite 355]
12.4.3 - Experimental [Seite 356]
12.4.3.1 - Preparation of Highly Active Manganese (Mn) [Seite 356]
12.4.3.2 - Typical Preparation of Benzylic Manganese Halides and Their Coupling Reactions with Benzoyl Chlorides to Give Ketones (2a-2l) [Seite 357]
12.4.3.3 - Typical Procedure for the Cross-Coupling Reactions of Benzyl Manganese Mesylates [Seite 357]
12.4.3.4 - Preparation of Alcohols from the Reactions of Benzylic Manganese Halides with Aldehydes and Ketones (3a-3i) [Seite 357]
12.4.3.5 - Typical Preparation of Benzylic Manganese Phosphates and Their Cross-Coupling Reactions [Seite 358]
12.4.3.6 - Homocoupling Reactions of Functionalized Benzyl Halides [Seite 358]
12.4.3.7 - Typical Procedure for the Coupling Reaction of (1f) with Aldehydes and Acid Chlorides (13a-13d, 14-18) [Seite 358]
12.4.3.8 - Typical Preparation of Functionalized Benzylic Manganese Halides and Their Cross-Coupling Reactions with Aryl Iodides under a Palladium Catalyst [Seite 359]
12.5 - 8.5 Preparation and Coupling Reactions of Thienylmanganese Halides [Seite 359]
12.6 - 8.6 Synthesis of ??Hydroxy Esters Using Active Manganese [Seite 363]
12.7 - 8.7 Reductive Coupling of Carbonyl-Containing Compounds and Imines Using Reactive Manganese [Seite 367]
12.7.1 - Results and Discussion [Seite 371]
12.7.1.1 - Reductive Coupling Reactions of Aryl Aldehydes [Seite 371]
12.7.1.2 - Reductive Coupling Reactions of Aryl Ketones [Seite 373]
12.7.1.3 - Reductive Coupling of Aldimines [Seite 374]
12.7.1.4 - Conclusions [Seite 374]
12.7.2 - Typical Experimental Procedures [Seite 374]
12.7.2.1 - Preparation of Highly Reactive Manganese (Mn*) [Seite 374]
12.7.2.2 - A Typical Procedure for the Preparation of 1,2-Diols (2a-2h) from the Reactions of Aryl Aldehydes with Mn* [Seite 375]
12.7.2.3 - Typical Procedure for the Preparation of 1,2-Diols from the Reaction of Aryl Ketones with Mn* [Seite 375]
12.7.2.4 - Reductive Coupling Reaction of Aldimines (13 and 15) into Vicinal Diamines (14 and 16) [Seite 375]
12.8 - 8.8 Preparation of Heteroarylmanganese Reagents and Their Cross-Coupling Chemistry [Seite 375]
12.9 - References [Seite 380]
13 - Chapter 9 Calcium [Seite 391]
13.1 - 9.1 Preparation of Rieke Calcium [Seite 391]
13.2 - 9.2 Oxidative Addition Reactions of Rieke Calcium with Organic Halides and Some Subsequent Reactions [Seite 392]
13.2.1 - Grignard-Type Reactions with Highly Reactive Calcium [Seite 392]
13.3 - 9.3 Preparation and Reaction of Calcium Cuprate Reagents [Seite 393]
13.4 - 9.4 Preparation and Reactions of Calcium Metallocycles [Seite 397]
13.4.1 - Typical Procedure for the Preparation of Active Calcium [Seite 400]
13.4.2 - Typical Grignard-Type Reaction [Seite 400]
13.4.3 - Typical Ketone Formation Reaction [Seite 400]
13.4.4 - Typical Conjugate 1,4-Addition Reaction [Seite 401]
13.4.5 - Typical Reaction of the Calcium Complex of 1,3-Diene [Seite 401]
13.5 - 9.5 Synthesis of Polyphenylcarbynes Using Highly Reactive Calcium, Barium, and Strontium: A Precursor for Diamond?like Carbon [Seite 402]
13.6 - 9.6 Chemical Modification of Halogenated Polystyrenes Using Rieke Calcium or Rieke Copper [Seite 406]
13.7 - References [Seite 408]
14 - Chapter 10 Barium [Seite 411]
14.1 - 10.1 Preparation of Rieke Barium [Seite 411]
14.2 - 10.2 Oxidative Addition of Rieke Barium to Allylic Halides: Preparation of Stereochemically Homogeneous Allylic Barium Reagents [Seite 412]
14.3 - References [Seite 414]
15 - Chapter 11 Iron [Seite 415]
15.1 - 11.1 Preparation of Highly Reactive Iron and Some Oxidative Addition Chemistry [Seite 415]
15.1.1 - Preparation of a Typical Iron Slurry [Seite 416]
15.1.2 - Preparation of Fe(C6F5)2(CO)2(C4H10O2)2 [Seite 416]
15.2 - References [Seite 417]
16 - Chapter 12 Palladium and Platinum [Seite 419]
16.1 - 12.1 Preparation of Highly Reactive Palladium and Platinum and Some Oxidative Addition Chemistry [Seite 419]
16.1.1 - Preparation of Slurries [Seite 421]
16.1.2 - Palladium Compounds [Seite 421]
16.1.3 - Platinum Compounds [Seite 422]
16.1.4 - Summary [Seite 422]
16.1.5 - Preparation of trans-[P(C2H5)3]2Pd(C6H5)I [Seite 423]
16.1.6 - Preparation of trans-[P(C2H5)3]2Pd(C6H5)Br [Seite 423]
16.1.7 - Preparation of trans-[P(C2H5)3]2Pd(C6H5)CN [Seite 424]
16.1.8 - Preparation of trans-[P(C2H5)3]2Pt(C6H5)I [Seite 424]
16.1.9 - Preparation of trans-[P(C2H5)3]2Pt(C6H5)Br [Seite 425]
16.2 - References [Seite 425]
17 - Chapter 13 Highly Reactive Uranium and Thorium [Seite 427]
17.1 - 13.1 Two Methods for Preparation of Highly Reactive Uranium and Thorium: Use of a Novel Reducing Agent Naphthalene Dianion [Seite 427]
17.1.1 - Results and Discussion [Seite 429]
17.1.2 - Conclusion [Seite 437]
17.1.3 - Preparation of Active Uranium in DME (1) [Seite 438]
17.1.4 - Reaction of (1) with 1,3-Butadiene [Seite 438]
17.1.5 - Preparation of [(TMEDA)Li]2[Nap] (2) [Seite 438]
17.1.6 - Preparation of Active Uranium in Hydrocarbon Solvents (3) [Seite 439]
17.1.7 - Reaction of (3) with Ketones [Seite 439]
17.1.8 - Reaction of (3) with Pinacols [Seite 439]
17.1.9 - Preparation of (p-CH3C6H4)2COHCOH(p-CH3C6H4)2 [94] [Seite 440]
17.2 - References [Seite 440]
18 - Chapter 14 Aluminum [Seite 445]
18.1 - 14.1 Preparation of Highly Reactive Aluminum and Reaction with Aryl Halides [Seite 445]
18.1.1 - Experimental [Seite 446]
18.2 - References [Seite 447]
19 - Chapter 15 Cobalt [Seite 449]
19.1 - 15.1 Two Methods for Preparing Rieke Cobalt: Reaction with CO and Also Fischer-Tropsch Chemistry [Seite 449]
19.1.1 - Preparation of Cobalt Powder (1) [Seite 451]
19.1.2 - Preparation of Cobalt Powder (2) [Seite 451]
19.1.3 - Preparation of Co2(CO)8 from Activated Cobalt [Seite 452]
19.1.3.1 - Method 1 [Seite 452]
19.1.3.2 - Method 2 [Seite 452]
19.1.4 - Reaction of Co with Synthesis Gas [Seite 453]
19.1.4.1 - Method 1 [Seite 453]
19.1.4.2 - Method 2 [Seite 454]
19.1.5 - Hydrolysis of Active Cobalt [Seite 454]
19.1.6 - Reaction of Dry Cobalt Powders with CO [Seite 456]
19.1.7 - Reaction of Cobalt with Aromatic Nitro Compounds [Seite 457]
19.1.7.1 - Nitrobenzene [Seite 457]
19.1.7.2 - 1-Iodo-4-Nitrobenzene [Seite 458]
19.1.7.3 - 1,2-Dinitrobenzene [Seite 459]
19.1.8 - Reaction of Cobalt with C6F5I: Preparation of (C6F5)2Co?2PEt3 [Seite 459]
19.1.9 - Reaction with Benzyl Bromide [Seite 459]
19.1.10 - Reaction with Phenyl Halides: Phenyl Iodide [Seite 460]
19.1.10.1 - Method 1 [Seite 460]
19.1.10.2 - Method 2 [Seite 460]
19.1.11 - Preparation of Tetraphenylethylene [Seite 460]
19.1.11.1 - Method 1 [Seite 460]
19.1.11.2 - Method 2 [Seite 460]
19.1.11.3 - Method 3 [Seite 461]
19.1.12 - Reaction of Cobalt with Diiodomethane [Seite 461]
19.2 - References [Seite 461]
20 - Chapter 16 Chromium [Seite 463]
20.1 - 16.1 Preparation of Highly Reactive Chromium Metal and Its Reaction with CO to Yield Cr(CO)6 [Seite 463]
20.1.1 - Experimental [Seite 465]
20.1.1.1 - Preparation of Cr(CO)6 from Chromium Powder [Seite 465]
20.1.1.2 - Preparation of Cr(CO)6 by Reduction with Activated Magnesium [Seite 465]
20.1.1.3 - Extraction of Chromium Powder [Seite 465]
20.2 - References [Seite 466]
21 - Index [Seite 467]
22 - EULA [Seite 483]