The mechanism of alkene addition to a nickel bis(dithiolene) complex

The role of the reduced metal complex

Li Dang, Mohamed F. Shibl, Xinzheng Yang, Aiman Alak, Daniel J. Harrison, Ulrich Fekl, Edward Brothers, Michael B. Hall

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The binding of an alkene by Ni(tfd) 2 [tfd = S 2C 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.

Original languageEnglish
Pages (from-to)4481-4484
Number of pages4
JournalJournal of the American Chemical Society
Volume134
Issue number10
DOIs
Publication statusPublished - 14 Mar 2012

Fingerprint

Coordination Complexes
Alkenes
Metal complexes
Nickel
Olefins
Anions
Negative ions
Decomposition
Discrete Fourier transforms
Ligands
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

The mechanism of alkene addition to a nickel bis(dithiolene) complex : The role of the reduced metal complex. / Dang, Li; Shibl, Mohamed F.; Yang, Xinzheng; Alak, Aiman; Harrison, Daniel J.; Fekl, Ulrich; Brothers, Edward; Hall, Michael B.

In: Journal of the American Chemical Society, Vol. 134, No. 10, 14.03.2012, p. 4481-4484.

Research output: Contribution to journalArticle

Dang, Li ; Shibl, Mohamed F. ; Yang, Xinzheng ; Alak, Aiman ; Harrison, Daniel J. ; Fekl, Ulrich ; Brothers, Edward ; Hall, Michael B. / The mechanism of alkene addition to a nickel bis(dithiolene) complex : The role of the reduced metal complex. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 10. pp. 4481-4484.
@article{97033b07c1d14cde87455be89f9769f9,
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 2C 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.",
author = "Li Dang and Shibl, {Mohamed F.} and Xinzheng Yang and Aiman Alak and Harrison, {Daniel J.} and Ulrich Fekl and Edward Brothers and Hall, {Michael B.}",
year = "2012",
month = "3",
day = "14",
doi = "10.1021/ja2107965",
language = "English",
volume = "134",
pages = "4481--4484",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - The mechanism of alkene addition to a nickel bis(dithiolene) complex

T2 - The role of the reduced metal complex

AU - Dang, Li

AU - Shibl, Mohamed F.

AU - Yang, Xinzheng

AU - Alak, Aiman

AU - Harrison, Daniel J.

AU - Fekl, Ulrich

AU - Brothers, Edward

AU - Hall, Michael B.

PY - 2012/3/14

Y1 - 2012/3/14

N2 - The binding of an alkene by Ni(tfd) 2 [tfd = S 2C 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.

AB - The binding of an alkene by Ni(tfd) 2 [tfd = S 2C 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.

UR - http://www.scopus.com/inward/record.url?scp=84863229194&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84863229194&partnerID=8YFLogxK

U2 - 10.1021/ja2107965

DO - 10.1021/ja2107965

M3 - Article

VL - 134

SP - 4481

EP - 4484

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 10

ER -