Enhanced descriptions from Syndetics:

Provides historical perspective as well as current data Abundantly illustrated with figures redrawn from literature data Covers all pertinent theory and physical chemistry Catalytic and chemotherapeutic applications are included

Table of contents provided by Syndetics

• Introduction and Survey
• 1.1 Prolog (p. 1)
• 1.1.1 From Werner to the new transition metal chemistry (p. 1)
• 1.1.2 Prior to about 1963 (p. 2)
• 1.2 How It All Began (p. 3)
• 1.2.1 Rhenium chemistry from 1963 to 1965 (p. 3)
• 1.2.2 The recognition of the quadruple bond (p. 7)
• 1.2.3 Initial work on other elements (p. 8)
• 1.3 An Overview of the Multiple Bonds (p. 12)
• 1.3.1 A qualitative picture of the quadruple bond (p. 13)
• 1.3.2 Bond orders less than four (p. 15)
• 1.3.3 Oxidation states (p. 15)
• 1.4 Growth of the Field (p. 16)
• 1.5 Going Beyond Two (p. 19)
• Complexes of the Group 5 Elements
• 2.1 General Remarks (p. 23)
• 2.2 Divanadium Compounds (p. 23)
• 2.2.1 Triply-bonded divanadium compounds (p. 24)
• 2.2.2 Metal-metal vs metal-ligand bonding (p. 27)
• 2.2.3 Divanadium compounds with the highly reduced V 2 3+ core (p. 27)
• 2.3 Diniobium Compounds (p. 29)
• 2.3.1 Diniobium paddlewheel complexes (p. 29)
• 2.3.2 Diniobium compounds with calix[4]arene ligands and related species (p. 31)
• 2.4 Tantalum (p. 32)
• Chromium Compounds
• 3.1 Dichromium Tetracarboxylates (p. 35)
• 3.1.1 History and preparation (p. 35)
• 3.1.2 Properties of carboxylate compounds (p. 38)
• 3.1.3 Unsolvated Cr 2 (O 2 CR) 4 compounds (p. 40)
• 3.2 Other Paddlewheel Compounds (p. 43)
• 3.2.1 The first 'supershort' bonds (p. 43)
• 3.2.2 2-Oxopyridinate and related compounds (p. 47)
• 3.2.3 Carboxamidate compounds (p. 50)
• 3.2.4 Amidinate compounds (p. 52)
• 3.2.5 Guanidinate compounds (p. 56)
• 3.3 Miscellaneous Dichromium Compounds (p. 57)
• 3.3.1 Compounds with intramolecular axial interactions (p. 57)
• 3.3.2 Compounds with Cr-C bonds (p. 60)
• 3.3.3 Other pertinent results (p. 61)
• 3.4 Concluding Remarks (p. 65)
• Molybdenum Compounds
• 4.1 Dimolybdenum Bridged by Carboxylates or Other O,O Ligands (p. 69)
• 4.1.1 General remarks (p. 69)
• 4.1.2 Mo 2 (O 2 CR) 4 compounds (p. 70)
• 4.1.3 Other compounds with bridging carboxyl groups (p. 79)
• 4.1.4 Paddlewheels with other O,O anion bridges (p. 92)
• 4.2 Paddlewheel Compounds with O,N, N,N and Other Bridging Ligands (p. 95)
• 4.2.1 Compounds with anionic O,N bridging ligands (p. 95)
• 4.2.2 Compounds with anionic N,N bridging ligands (p. 98)
• 4.2.3 Compounds with miscellaneous other anionic bridging ligands (p. 103)
• 4.3 Non-Paddlewheel Mo 2 4+ Compounds (p. 105)
• 4.3.1 Mo 2 X 8 4- and Mo 2 X 6 (H 2 O) 2 2- compounds (p. 105)
• 4.3.2 [Mo 2 X 8 H] 3- compounds (p. 108)
• 4.3.3 Other aspects of dimolybdenum halogen compounds (p. 109)
• 4.3.4 M 2 X 4 L 4 and Mo 2 X 4 (LL) 2 compounds (p. 111)
• 4.3.5 Cationic complexes of Mo 2 4+ (p. 130)
• 4.3.6 Complexes of Mo 2 4+ with macrocyclic, polydentate and chelate ligands (p. 132)
• 4.3.7 Alkoxide compounds of the types Mo 2 (OR) 4 L 4 and Mo 2 (OR) 4 (LL) 2 (p. 134)
• 4.4 Other Aspects of Mo 2 4+ Chemistry (p. 136)
• 4.4.1 Cleavage of Mo 2 4+ compounds (p. 136)
• 4.4.2 Redox behavior of Mo 2 4+ compounds (p. 137)
• 4.4.3 Hydrides and organometallics (p. 142)
• 4.4.4 Heteronuclear Mo-M compounds (p. 145)
• 4.4.5 An overview of Mo-Mo bond lengths in Mo 2 4+ compounds (p. 148)
• 4.5 Higher-order Arrays of Dimolybdenum Units (p. 148)
• 4.5.1 General concepts (p. 148)
• 4.5.2 Two linked pairs with carboxylate spectator ligands (p. 154)
• 4.5.3 Two linked pairs with nonlabile spectator ligands (p. 155)
• 4.5.4 Squares: four linked pairs (p. 160)
• 4.5.5 Loops: two pairs doubly linked (p. 162)
• 4.5.6 Rectangular cyclic quartets (p. 164)
• 4.5.7 Other structural types (p. 166)
• Tungsten Compounds
• 5.1 Multiple Bonds in Ditungsten Compounds (p. 183)
• 5.2 The W 2 4+ Tetracarboxylates (p. 183)
• 5.3 W 2 4+ Complexes Containing Anionic Bridging Ligands Other Than Carboxylate (p. 189)
• 5.4 W 2 4+ Complexes without Bridging Ligands (p. 191)
• 5.4.1 Compounds coordinated by only anionic ligands (p. 191)
• 5.4.2 Compounds coordinated by four anionic ligands and four neutral ligands (p. 192)
• 5.5 Multiple Bonds in Heteronuclear Dimetal Compounds of Molybdenum and Tungsten (p. 196)
• 5.6 Paddlewheel Compounds with W 2 5+ or W 2 6+ Cores (p. 197)
• X 3 M ≡ MX 3 Compounds of Molybdenum and Tungsten
• 6.1 Introduction (p. 203)
• 6.2 Homoleptic X 3 M ≡ MX 3 Compounds (p. 204)
• 6.2.1 Synthesis and characterization of homoleptic M 2 X 6 compounds (p. 204)
• 6.2.2 Bonding in M 2 X 6 compounds (p. 208)
• 6.2.3 X 3 M ≡ MX 3 Compounds as Molecular Precursors to Extended Solids (p. 210)
• 6.3 M 2 X 2 (NMe 2 ) 4 and M 2 X 4 (NMe 2 ) 2 Compounds (p. 210)
• 6.4 Other M 2 X 2 Y 4 , M 2 X 6-n Y n and Related Compounds (p. 212)
• 6.4.1 Mo 2 X 2 (CH 2 SiMe 3 ) 4 compounds (p. 215)
• 6.4.2 1,2-M 2 R 2 (NMe 2 ) 4 compounds and their derivatives (p. 217)
• 6.5 M 4 Complexes: Clusters or Dimers? (p. 218)
• 6.5.1 Molybdenum and tungsten twelve-electron clusters M 4 (OR) 12 (p. 218)
• 6.5.2 M 4 X 4 (OPr i ) 8 (X = Cl, Br) and Mo 4 Br 3 (OPr i ) 9 (p. 220)
• 6.5.3 W 4 (p-tolyl) 2 (OPr i ) 10 (p. 221)
• 6.5.4 W 4 O(X)(OPr i ) 9 , (X = Cl or OPr i ) (p. 221)
• 6.5.5 K(18-crown-6) 2 Mo 4 (¿ 4 -H)(OCH 2 Bu t ) 12 (p. 221)
• 6.5.6 Linked M 4 units containing localized MM triple bonds (p. 222)
• 6.6 M 2 X 6 L, M 2 X 6 L 2 and Related Compounds (p. 223)
• 6.6.1 Mo 2 (CH 2 Ph) 2 (OPr i ) 4 (PMe 3 ) and [Mo 2 (OR) 7 ] - (p. 223)
• 6.6.2 M 2 (OR) 6 L 2 compounds and their congeners (p. 224)
• 6.6.3 Amido-containing compounds (p. 226)
• 6.6.4 Mo 2 Br 2 (CHSiMe 3 ) 2 (PMe 3 ) 4 (p. 228)
• 6.6.5 Calix[4]arene complexes (p. 228)
• 6.7 Triple Bonds Uniting Five- and Six-Coordinate Metal Atoms (p. 229)
• 6.8 Redox Reactions at the M 2 6+ Unit (p. 230)
• 6.9 Organometallic Chemistry of M 2 (OR) 6 and Related Compounds (p. 232)
• 6.9.1 Carbonyl adducts and their products (p. 232)
• 6.9.2 Isocyanide complexes (p. 234)
• 6.9.3 Reactions with alkynes (p. 234)
• 6.9.4 Reactions with C≡N bonds (p. 236)
• 6.9.5 Reactions with C=C bonds (p. 237)
• 6.9.6 Reactions with H 2 (p. 240)
• 6.9.7 Reactions with organometallic compounds (p. 241)
• 6.9.8 (¿-C 5 H 4 R) 2 W 2 X 4 compounds where R = Me, Pr i and X = Cl, Br (p. 241)
• 6.10 Conclusion (p. 242)
• Technetium Compounds
• 7.1 Synthesis and Properties of Technetium (p. 251)
• 7.2 Preparation of Dinuclear and Polynuclear Technetium Compounds (p. 252)
• 7.3 Bonds of Order 4 and 3.5 (p. 252)
• 7.4 Tc 2 6+ and Tc 2 5+ Carboxylates and Related Species with Bridging Ligands (p. 257)
• 7.5 Bonds of Order 3 (p. 261)
• 7.6 Hexanuclear and Octanuclear Technetium Clusters (p. 265)
• Rhenium Compounds
• 8.1 The Last Naturally Occurring Element to Be Discovered (p. 271)
• 8.2 Synthesis and Structure of the Octachlorodirhenate(III) Anion (p. 273)
• 8.3 Synthesis and Structure of the Other Octahalodirhenate(III) Anions (p. 278)
• 8.4 Substitution Reactions of the Octahalodirhenate(III) Anions that Proceed with Retention of the Re 2 6+ Core (p. 280)
• 8.4.1 Monodentate anionic ligands (p. 280)
• 8.4.2 The dirhenium(III) carboxylates (p. 282)
• 8.4.3 Other anionic ligands (p. 292)
• 8.4.4 Neutral ligands (p. 298)
• 8.5 Dirhenium Compounds with Bonds of Order 3.5 and 3 (p. 302)
• 8.5.1 The first metal-metal triple bond: Re 2 Cl 5 (CH 3 SCH 2 CH 2 SCH 3 ) 2 and related species (p. 302)
• 8.5.2 Simple electron-transfer chemistry involving the octahalodirhenate(III) anions and related species that contain quadruple bonds (p. 303)
• 8.5.3 Oxidation of [Re 2 X 8 ] 2- to the nonahalodirhenate anions [Re 2 X 9 ] n- (n = 1 or 2) (p. 307)
• 8.5.4 Re 2 5+ and Re 2 4+ halide complexes that contain phosphine ligands (p. 309)
• 8.5.5 Other Re 2 5+ and Re 2 4+ complexes (p. 359)
• 8.5.6 Other dirhenium compounds with triple bonds (p. 360)
• 8.6 Dirhenium Compounds with Bonds of Order Less than 3 (p. 361)
• 8.7 Cleavage of Re-Re Multiple Bonds by o-donor and ¿-acceptor Ligands (p. 361)
• 8.7.1 ¿-Donor ligands (p. 362)
• 8.7.2 J¿-Acceptor ligands (p. 363)
• 8.8 Other Types of Multiply Bonded Dirhenium Compounds (p. 363)
• 8.9 Postscript on Recent Developments (p. 364)
• Ruthenium Compounds
• 9.1 Introduction (p. 377)
• 9.2 Ru 2 5+ Compounds (p. 378)
• 9.2.1 Ru 2 5+ compounds with O,O′-donor bridging ligands (p. 382)
• 9.2.2 Ru 2 5+ compounds with N,O-donor bridging ligands (p. 391)
• 9.2.3 Ru 2 5+ compounds with N,N′-donor bridging ligands (p. 396)
• 9.3 Ru 2 4+ Compounds (p. 404)
• 9.3.1 Ru 2 4+ compounds with O,O′-donor bridging ligands (p. 405)
• 9.3.2 Ru 2 4+ compounds with N,O-donor bridging ligands (p. 409)
• 9.3.3 Ru 2 4+ compounds with N,N′-donor bridging ligands (p. 411)
• 9.4 Ru 2 6+ Compounds (p. 414)
• 9.4.1 Ru 2 6+ compounds with O,O′-donor bridging ligands (p. 415)
• 9.4.2 Ru 2 6+ compounds with N,N′-donor bridging ligands (p. 416)
• 9.5 Compounds with Macrocyclic Ligands (p. 422)
• 9.6 Applications (p. 422)
• 9.6.1 Catalytic activity (p. 422)
• 9.6.2 Biological importance (p. 423)
• Osmium Compounds
• 10.1 Syntheses, Structures and Reactivity of Os 2 6+ Compounds (p. 431)
• 10.2 Syntheses and Structures of Os 2 5+ Compounds (p. 437)
• 10.3 Syntheses and Structures of Other Os 2 Compounds (p. 438)
• 10.4 Magnetism, Electronic Structures, and Spectroscopy (p. 439)
• 10.5 Concluding Remarks (p. 444)
• Iron, Cobalt and Iridium Compounds
• 11.1 General Remarks (p. 447)
• 11.2 Di-iron Compounds (p. 447)
• 11.3 Dicobalt Compounds (p. 451)
• 11.3.1 Tetragonal paddlewheel compounds (p. 451)
• 11.3.2 Trigonal paddlewheel compounds (p. 453)
• 11.3.3 Dicobalt compounds with unsupported bonds (p. 454)
• 11.3.4 Compounds with chains of cobalt atoms (p. 455)
• 11.4 Di-iridium Compounds (p. 455)
• 11.4.1 Paddlewheel compounds and related species (p. 455)
• 11.4.2 Unsupported Ir-Ir bonds (p. 458)
• 11.4.3 Other species with Ir-Ir bonds (p. 459)
• 11.4.4 Iridium blues (p. 461)
• Rhodium Compounds
• 12.1 Introduction (p. 465)
• 12.2 Dirhodium Tetracarboxylato Compounds (p. 466)
• 12.2.1 Preparative methods and classification (p. 466)
• 12.2.2 Structural studies (p. 469)
• 12.3 Other Dirhodium Compounds Containing Bridging Ligands (p. 493)
• 12.3.1 Complexes with fewer than four carboxylate bridging groups (p. 493)
• 12.3.2 Complexes supported by hydroxypyridinato, carboxamidato and other (N, O) donor monoanionic bridging groups (p. 505)
• 12.3.3 Complexes supported by amidinato and other (N, N) donor bridging groups (p. 512)
• 12.3.4 Complexes supported by sulfur donor bridging ligands (p. 521)
• 12.3.5 Complexes supported by phosphine and (P, N) donor bridging ligands (p. 524)
• 12.3.6 Complexes supported by carbonate, sulfate and phosphate bridging groups (p. 527)
• 12.4 Dirhodium Compounds with Unsupported Rh-Rh Bonds (p. 528)
• 12.4.1 The dirhodium(II) aquo ion (p. 528)
• 12.4.2 The [Rh 2 (NCR) 10 ] 4+ cations (p. 529)
• 12.4.3 Complexes with chelating and macrocyclic nitrogen ligands (p. 530)
• 12.5 Other Dirhodium Compounds (p. 533)
• 12.5.1 Complexes with isocyanide ligands (p. 533)
• 12.5.2 Rhodium blues (p. 536)
• 12.6 Reactions of Rh 2 4+ Compounds (p. 540)
• 12.6.1 Oxidation to Rh 2 5+ and Rh 2 6+ species (p. 540)
• 12.6.2 Cleavage of the Rh-Rh bond (p. 547)
• 12.7 Applications of Dirhodium Compounds (p. 547)
• 12.7.1 Catalysis (p. 547)
• 12.7.2 Supramolecular arrays based on dirhodium building blocks (p. 548)
• 12.7.3 Biological applications of dirhodium compounds (p. 555)
• 12.7.4 Photocatalytic reactions (p. 566)
• 12.7.5 Other applications (p. 567)
• Chiral Dirhodium(II) Catalysts and Their Applications
• 13.1 Introduction (p. 591)
• 13.2 Synthetic and Structural Aspects of Chiral Dirhodium(II) Carboxamidates (p. 591)
• 13.3 Synthetic and Structural Aspects of Dirhodium(II) Complexes Bearing Orthometalated Phosphines (p. 599)
• 13.4 Dirhodium(II) Compounds as Catalysts (p. 605)
• 13.5 Catalysis of Diazo Decomposition (p. 607)
• 13.6 Chiral Dirhodium(II) Carboxylates (p. 609)
• 13.7 Chiral Dirhodium(II) Carboxamidates (p. 611)
• 13.8 Catalytic Asymmetric Cyclopropanation and Cyclopropenation (p. 613)
• 13.8.1 Intramolecular reactions (p. 613)
• 13.8.2 Intermolecular reactions (p. 616)
• 13.8.3 Cyclopropenation (p. 617)
• 13.8.4 Macrocyclization (p. 617)
• 13.9 Metal Carbene Carbon-Hydrogen Insertion (p. 619)
• 13.9.1 Intramolecular reactions (p. 619)
• 13.9.2 Intermolecular reactions (p. 624)
• 13.10 Catalytic Ylide Formation and Reactions (p. 624)
• 13.11 Additional Transformations of Diazo Compounds Catalyzed by Dirhodium(II) (p. 626)
• 13.12 Silicon-Hydrogen Insertion (p. 626)
• Nickel, Palladium and Platinum Compounds
• 14.1 General Remarks (p. 633)
• 14.2 Dinickel Compounds (p. 633)
• 14.3 Dipalladium Compounds (p. 634)
• 14.3.1 A singly bonded Pd 2 6+ species (p. 634)
• 14.3.2 Chemistry of Pd 2 5+ and similar species (p. 635)
• 14.3.3 Other compounds with Pd-Pd interactions (p. 636)
• 14.4 Diplatinum Compounds (p. 636)
• 14.4.1 Complexes with sulfate and phosphate bridges (p. 642)
• 14.4.2 Complexes with pyrophosphite and related ligands (p. 644)
• 14.4.3 Complexes with carboxylate, formamidinate and related ligands (p. 646)
• 14.4.4 Complexes containing monoanionic bridging ligands with N,O and N,S donor sets (p. 648)
• 14.4.5 Unsupported Pt-Pt bonds (p. 656)
• 14.4.6 Dinuclear Pt 2 5+ species (p. 657)
• 14.4.7 The platinum blues (p. 658)
• 14.4.6 Other compounds (p. 661)
• Extended Metal Atom Chains
• 15.1 Overview (p. 669)
• 15.2 EMACs of Chromium (p. 671)
• 15.3 EMACs of Cobalt (p. 686)
• 15.4 EMACs of Nickel and Copper (p. 694)
• 15.5 EMACs of Ruthenium and Rhodium (p. 701)
• 15.6 Other Metal Atom Chains (p. 702)
• Physical, Spectroscopic and Theoretical Results
• 16.1 Structural Correlations (p. 707)
• 16.1.1 Bond orders and bond lengths (p. 707)
• 16.1.2 Internal rotation (p. 710)
• 16.1.3 Axial ligands (p. 712)
• 16.1.4 Comparison of second and third transition series homologs (p. 713)
• 16.1.5 Disorder in crystals (p. 715)
• 16.1.6 Rearrangements of M 2 X 8 type molecules (p. 718)
• 16.1.7 Diamagnetic anisotropy of M-M multiple bonds (p. 720)
• 16.2 Thermodynamics (p. 721)
• 16.2.1 Thermochemical data (p. 721)
• 16.2.2 Bond energies (p. 722)
• 16.3 Electronic Structure Calculations (p. 724)
• 16.3.1 Background (p. 724)
• 16.3.2 [M 2 X 8 ] n- and M 2 X 4 (PR 3 ) 4 species (p. 725)
• 16.3.3 The M 2 (O 2 CR) 4 (M = Cr, Mo, W) molecules (p. 728)
• 16.3.4 M 2 (O 2 CR) 4 R′ 2 (M = Mo, W) compounds (p. 729)
• 16.3.5 Dirhodium species (p. 731)
• 16.3.6 Diruthenium compounds (p. 732)
• 16.3.7 M 2 X 6 molecules (M = Mo, W) (p. 733)
• 16.3.8 Other calculations (p. 738)
• 16.4 Electronic Spectra (p. 738)
• 16.4.1 Details of the ¿ manifold of states (p. 739)
• 16.4.2 Observed ¿ → ¿* transitions (p. 744)
• 16.4.3 Other electronic absorption bands of Mo 2 , W 2 , Tc 2 and Re 2 species (p. 751)
• 16.4.4 Spectra of Rh 2 , Pt 2 , Ru 2 and Os 2 compounds (p. 756)
• 16.4.5 CD and ORD spectra (p. 758)
• 16.4.6 Excited state distortions inferred from vibronic structure (p. 760)
• 16.4.7 Emission spectra and photochemistry (p. 762)
• 16.5 Photoelectron Spectra (p. 766)
• 16.5.1 Paddlewheel molecules (p. 766)
• 16.5.2 Other tetragonal molecules (p. 772)
• 16.5.3 M 2 X 6 molecules (p. 773)
• 16.5.4 Miscellaneous other PES results (p. 774)
• 16.6 Vibrational Spectra (p. 775)
• 16.6.1 M-M stretching vibrations (p. 775)
• 16.6.2 M-L stretching vibrations (p. 781)
• 16.7 Other types of Spectra (p. 783)
• 16.7.1 Electron Paramagnetic Resonance (p. 783)
• 16.7.2 X-Ray spectra, EXAFS, and XPS (p. 785)
• Abbreviations (p. 797)
• Index (p. 811)