By Stephen J. Lippard
Coupling Reactions of Terminal Two-Faced pi Ligands and similar Cleavage response (A. Mayr & C. Bastos).
The Interface of Nanoscale Inclusion Chemistry (G. Stucky).
Polydentate Phosphines: Their Synthesis, Structural facets and chosen purposes (F. Cotton & B. Hong).
Iron- and Cobalt-Induced Activation of Hydrogen Peroxide and Dioxygen for the Selective Oxidation/Dehydrogenation and Oxygenation of natural Molecules (A. Sobkowiak, et al.).
Sterically tough Fluorinated Substituents and steel Fluorides with cumbersome Ligands (M. Witt & H. Roesky).
Coordination Chemistry of Thionitrosyl (NS), Thiazate (NSO?-), Disulphidothionitrate (S3N?-), Sulfur Monoxide (SO) and Disulfur Monoxide (S2O) Ligands (K. Pandey).
Thermodynamics of Ligand Binding and trade in Organometallic Reactions (C. Hoff).Content:
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Additional info for Progress in Inorganic Chemistry, Volume 40
BuCO. PhCHfiO. 4-OMePh (48) We obtained several types of ynol-derived metal complexes by alkylation, acylation, and silylation of the v2-ketenyl ligands in complexes 59 and 60, Eq. 48 (59,64,and unpublished results). Protonation of ketenyl complex 59, however, does not afford the expected ynol complex, but the thioaldehyde complex 64, Eq. 49 (unpublished results). Presumably, the ynol tungsten complex R - Me, Ph W(S,CNEt,),(PhCCOH)(CO) is formed upon protonation, but decomposes to the thioaldehyde complex 64.
Most significantly, formation of the aminoalkyne complex is favored by the presence of H,O or CH,OH. This observation led to the development of a high-yield synthesis of 96 by reaction of 94 with HCI in CH30H as the solvent. The pathway of formation of the nitrilium ligand was postulated to involve a second protonation of the alkylidene ligand followed by migration of the generated benzyl ligand to coordinated isocyanide. The formation of the aminoalkyne ligand requires a formal proton transfer from the alkylidene carbon to the isocyanide nitrogen atom.
It was found that formation of the aminoalkyne ligand is faster in the presence of chloride, forming 96, than in the presence of trifluoromethanesulfonate, forming 98. Thus, the coupling of the alkylidyne ligand and the protonated isocyanide ligand may be promoted by the addition of a nucleophile to the metal center. The fact that the aminoalkyne complex is formed in the absence of chloride ions, that is, with trifluoromethanesulfonate as the coordinating ligand, however, indicates that a strongly nu- 38 ANDREAS MAYR AND CECILIA M .