title: Synthesis, structure, and alpha-elimination chemistry of hafnocene triarylstannyl complexes.
abstract: New hafnocene triarylstannyl complexes were prepared and were shown to undergo clean thermal decompositions via alpha-aryl-elimination to produce the corresponding stannylene and a hafnocene aryl complex. The rate of the decomposition is highly dependent on the nature of the ancillary ligand, with the stabilities of the CpCp*Hf(SnPh(3))X compounds following the order X = NMe(2) > Np (alpha-agostic) > OMe > Cl > Me. Mechanistic information suggests that alpha-aryl-elimination may be viewed as a concerted process involving nucleophilic attack of the migrating aryl group onto the electrophilic metal center.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
authors.forename: Nathan R
authors.initials: NR
authors.lastname: Neale
authors.forename: T Don
authors.initials: TD
authors.lastname: Tilley
mesh_terms: D018360:Crystallography, X-Ray; D006195:Hafnium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D009942:Organometallic Compounds; D006195:Hafnium