title: The mechanism of alkene addition to a nickel bis(dithiolene) complex: the role of the reduced metal complex.
abstract: The binding of an alkene by Ni(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] is one of the most intriguing ligand-based reactions. In the presence of the anionic, reduced metal complex, the primary product is an interligand adduct, while in the absence of the anion, dihydrodithiins and metal complex decomposition products are preferred. New kinetic (global analysis) and computational (DFT) data explain the crucial role of the anion in suppressing decomposition and catalyzing the formation of the interligand product through a dimetallic complex that appears to catalyze alkene addition across the Ni-S bond, leading to a lower barrier for the interligand adduct.
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, Texas 77842, United States.
authors.forename: Li
authors.initials: L
authors.lastname: Dang
authors.forename: Mohamed F
authors.initials: MF
authors.lastname: Shibl
authors.forename: Xinzheng
authors.initials: X
authors.lastname: Yang
authors.forename: Aiman
authors.initials: A
authors.lastname: Alak
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Harrison
authors.forename: Ulrich
authors.initials: U
authors.lastname: Fekl
authors.forename: Edward N
authors.initials: EN
authors.lastname: Brothers
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall