REACTIONS OF COMPLEX LIGANDS .41. THIOCARBENE COMPLEXES OF CHROMIUM AND TUNGSTEN - SIMPLE SYNTHESIS, INSERTION REACTION, ANNULATION REACTIONS

A series of novel thiocarbene complexes of chromium (I-XII) have been obtained in good yields in a one-pot reaction via acetylation of the lithium acylmetallates B in the presence of TMEDA and subsequent thiolysis. The photochemical decarbonylation of ortho-thioanisylcarbene complexes III, VIII and IX leads to cis-tetracarbonylcarbene-(C,S)-chelate complexes XIV-XVI. Carbene annulation of II with 1-hexyne yields naphthol XVII. The pentacarbonyl complexes (with the exception of ortho-substituted aryl compounds) react with 1-diethylaminopropyne to give the pentacarbonyl(diethylamino-E-vinylcarbene) complexes XVIII-XXIII via a highly stereoselective insertion of the alkyne into the metal-carbene bond.