Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process

Olena V. Zenkina, Amir Karton, Dalia Freeman, Linda J W Shimon, Jan M L Martin, Milko van der Boom

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Activation of a strong aryl-Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl-I containing substrates. η2-Coordination of Ni(PEt3)2 to the C=C moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl-halide bond activation process. This "ring- walking" process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl-halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-cc-pVDZ//PBE0/SDD level of theory.

Original languageEnglish
Pages (from-to)5114-5121
Number of pages8
JournalInorganic Chemistry
Volume47
Issue number12
DOIs
Publication statusPublished - Jun 16 2008

Fingerprint

walking
Nickel
Chemical activation
nickel
activation
halides
rings
Coordination Complexes
Density functional theory
insertion
Metals
density functional theory
Derivatives
Kinetics
kinetics
Substrates
metals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Zenkina, O. V., Karton, A., Freeman, D., Shimon, L. J. W., Martin, J. M. L., & van der Boom, M. (2008). Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process. Inorganic Chemistry, 47(12), 5114-5121. https://doi.org/10.1021/ic702289n

Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process. / Zenkina, Olena V.; Karton, Amir; Freeman, Dalia; Shimon, Linda J W; Martin, Jan M L; van der Boom, Milko.

In: Inorganic Chemistry, Vol. 47, No. 12, 16.06.2008, p. 5114-5121.

Research output: Contribution to journalArticle

Zenkina, OV, Karton, A, Freeman, D, Shimon, LJW, Martin, JML & van der Boom, M 2008, 'Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process', Inorganic Chemistry, vol. 47, no. 12, pp. 5114-5121. https://doi.org/10.1021/ic702289n
Zenkina, Olena V. ; Karton, Amir ; Freeman, Dalia ; Shimon, Linda J W ; Martin, Jan M L ; van der Boom, Milko. / Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 12. pp. 5114-5121.
@article{ed6a51572fe84864989c713ed617d4a6,
title = "Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process",
abstract = "Activation of a strong aryl-Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl-I containing substrates. η2-Coordination of Ni(PEt3)2 to the C=C moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl-halide bond activation process. This {"}ring- walking{"} process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl-halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-cc-pVDZ//PBE0/SDD level of theory.",
author = "Zenkina, {Olena V.} and Amir Karton and Dalia Freeman and Shimon, {Linda J W} and Martin, {Jan M L} and {van der Boom}, Milko",
year = "2008",
month = "6",
day = "16",
doi = "10.1021/ic702289n",
language = "English",
volume = "47",
pages = "5114--5121",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process

AU - Zenkina, Olena V.

AU - Karton, Amir

AU - Freeman, Dalia

AU - Shimon, Linda J W

AU - Martin, Jan M L

AU - van der Boom, Milko

PY - 2008/6/16

Y1 - 2008/6/16

N2 - Activation of a strong aryl-Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl-I containing substrates. η2-Coordination of Ni(PEt3)2 to the C=C moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl-halide bond activation process. This "ring- walking" process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl-halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-cc-pVDZ//PBE0/SDD level of theory.

AB - Activation of a strong aryl-Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl-I containing substrates. η2-Coordination of Ni(PEt3)2 to the C=C moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl-halide bond activation process. This "ring- walking" process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl-halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-cc-pVDZ//PBE0/SDD level of theory.

UR - http://www.scopus.com/inward/record.url?scp=84961985854&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84961985854&partnerID=8YFLogxK

U2 - 10.1021/ic702289n

DO - 10.1021/ic702289n

M3 - Article

VL - 47

SP - 5114

EP - 5121

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 12

ER -