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2.6 Product Class 6: Organometallic Complexes of Chromium,<br />
Molybdenum, and Tungsten without Carbonyl Ligands<br />
R. Poli and K. M. Smith<br />
2.6 Product Class 6: Organometallic Complexes of Chromium, Molybdenum,<br />
and Tungsten without Carbonyl Ligands .................................. 90<br />
2.6.1 Product Subclass 1: Metal–Carbene Complexes ........................... 90<br />
Synthesis of Product Subclass 1 ............................................ 91<br />
2.6.1.1 Method 1: By Æ-Hydrogen Elimination from Alkyl Complexes ........... 91<br />
2.6.1.1.1 Variation 1: Alkylation of Chloride Precursors ............................ 91<br />
2.6.1.1.2 Variation 2: Ligand Addition ............................................ 92<br />
2.6.1.1.3 Variation 3: Replacement of an Oxo or Imido Ligand ..................... 93<br />
2.6.1.1.4 Variation 4: Deprotonation with an External Base ........................ 94<br />
2.6.1.2 Method 2: By Stoichiometric Alkene Metathesis ........................ 94<br />
2.6.1.3 Method 3: By Carbene Transfer ........................................ 95<br />
2.6.1.4 Method 4: From Carbyne Complexes .................................. 96<br />
Applications of Product Subclass 1 in Organic Synthesis ..................... 97<br />
2.6.1.5 Method 5: Alkene Metathesis ......................................... 97<br />
2.6.1.5.1 Variation 1: Ring-Opening Metathesis Polymerization (ROMP) ............ 98<br />
2.6.1.5.2 Variation 2: Alkyne Polymerization ...................................... 98<br />
2.6.1.5.3 Variation 3: Ring-Closing Metathesis .................................... 99<br />
2.6.1.5.4 Variation 4: Other Selective Metathesis Processes ...................... 101<br />
2.6.1.6 Method 6: Carbonylmethylenation ................................... 102<br />
2.6.2 Product Subclass 2: Metal–Carbyne Complexes .......................... 103<br />
Synthesis of Product Subclass 2 ........................................... 104<br />
2.6.2.1 Method 1: By Æ,Æ-Hydrogen Elimination from Alkyl Complexes ........ 104<br />
2.6.2.2 Method 2: By Addition of Alkynes to Compounds with<br />
Metal-Metal Triple Bonds ................................. 105<br />
2.6.2.3 Method 3: By Stoichiometric Alkyne Metathesis ....................... 106<br />
2.6.2.4 Method 4: By Oxidation of Fischer-Type Carbyne Complexes ........... 107<br />
2.6.2.5 Method 5: By Rearrangement of Vinyl Complexes ..................... 108<br />
2.6.2.6 Method 6: By Other Rearrangement Processes ........................ 109<br />
Applications of Product Subclass 2 in Organic Synthesis .................... 110<br />
2.6.2.7 Method 7: Alkyne Metathesis ........................................ 110<br />
2.6.3 Product Subclass 3: Metal–ó-Alkyl and –ó-Aryl Homoleptic Complexes .. 110<br />
Synthesis of Product Subclass 3 ........................................... 111<br />
2.6.3.1 Method 1: By Transmetalation ........................................ 111<br />
2.6.4 Product Subclass 4: Metal–ó-Alkyl and –ó-Aryl Non-homoleptic Complexes 112<br />
Synthesis of Product Subclass 4 ........................................... 113<br />
2.6.4.1 Method 1: By Transmetalation ........................................ 113<br />
2.6.4.2 Method 2: By Oxidative Addition of Alkyl Halides ...................... 114<br />
2.6.4.2.1 Variation 1: One-Electron Oxidative Additions .......................... 114<br />
87
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