title: Hemilabile ligands in organolithium chemistry: substituent effects on lithium ion chelation.
abstract: The lithium diisopropylamide-mediated 1,2-elimination of 1-bromocyclooctene to provide cyclooctyne is investigated using approximately 50 potentially hemilabile polyethers and amino ethers. Rate laws for selected ligands reveal chelated monomer-based pathways. The dependence of the rates on ligand structure shows that anticipated rate accelerations based on the gem-dimethyl effect are nonexistent and that substituents generally retard the reaction. With the aid of semiempirical and DFT computational studies, the factors influencing chelation are discussed. It seems that severe buttressing within chelates of the substitutionally rich ligands precludes a net stabilization of the chelates relative to nonchelated (eta(1)-solvated) forms. One ligand-MeOCH(2)CH(2)NMe(2)-appears to promote elimination uniquely by a higher-coordinate monomer-based pathway.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853-1301, USA.
authors.forename: Antonio
authors.initials: A
authors.lastname: Ramírez
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: David B
authors.initials: DB
authors.lastname: Collum
mesh_terms: D002614:Chelating Agents / Q000737:chemistry; D018360:Crystallography, X-Ray; D034242:Cyclooctanes / Q000737:chemistry; D019856:Ethanolamine / Q000737:chemistry; D004988:Ethers, Cyclic / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D002614:Chelating Agents; D034242:Cyclooctanes; D004988:Ethers, Cyclic; D008024:Ligands; D009942:Organometallic Compounds; D019856:Ethanolamine; D008094:Lithium