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Title: Preparation and reductive elimination of (. eta. sup 3 -allyl)(aryl)nickel(II) complexes: Unusually facile. eta. sup 3 -allyl-aryl coupling on nickel having an 18-electron configuration

Abstract

The preparation and NMR spectral characterization of complexes of the type ({eta}{sup 3}-allyl)(aryl)(triphenylphosphine)nickel(II) (aryl = C{sub 6}H{sub 3}Cl{sub 2}-2,5, C{sub 6}F{sub 5}), 4, are described. Addition of PPh{sub 3} to a solution of 4 did not result in the formation of ({eta}{sup 1}-allyl)nickel intermediate as was deduced from {sup 1}H NMR measurements, in contrast to the ready conversion of ({eta}{sup 3}-allyl)palladium to ({eta}{sup 1}-allyl)palladium species. The (dichlorophenyl)nickel derivative underwent reductive elimination ca. 26 times as fast as the corresponding palladium complex. Addition of chelating diphosphine (Ph{sub 2}PCH{sub 2}CH{sub 2}PPh{sub 2}, (Z)-Ph{sub 2}PCH{double bond}CHPPh{sub 2}) to the solution of the above nickel complexes afforded stereochemically nonrigid 18-electron {eta}{sup 3}-allyl complexes, Ni({eta}{sup 3}-allyl)(aryl)(diphos), 5, which have been characterized by low-temperature {sup 1}H, {sup 13}C, and {sup 31}P NMR spectra for the C{sub 6}F{sub 5} analogues. This behavior is again different from that of the palladium analogue, which has an identical composition in which the 16-electron {eta}{sup 1}-allyl form is the ground-state structure. The kinetics of the reductive elimination of complexes 5 revealed that these undergo reductive elimination quite readily, with {Delta}H{sup {double dagger}} being ca. 60 kJ/mol lower than those values for the parent 16-electron counterparts 4. Also presented is evidence againstmore » the significant contribution of a short-lived 16-electron {eta}{sup 1}-allyl isomer of 5 to the enhanced reactivity with regard to the C-C coupling step in the diphosphine/allylnickel system.« less

Authors:
; ; ; ; ; ;  [1]
  1. Osaka Univ. (Japan)
Publication Date:
OSTI Identifier:
5943772
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 9:12; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; NICKEL COMPLEXES; CHEMICAL PREPARATION; REDUCTION; ACTIVATION ENERGY; ALKYNES; ARGON COMPLEXES; CHELATING AGENTS; CHEMICAL REACTION KINETICS; CHEMICAL SHIFT; DIENES; FLUORINATED AROMATIC HYDROCARBONS; HOMOGENEOUS CATALYSIS; LOW TEMPERATURE; MOLECULAR STRUCTURE; NMR SPECTRA; PHOSPHINES; REACTION INTERMEDIATES; AROMATICS; CATALYSIS; CHEMICAL REACTIONS; COMPLEXES; ENERGY; HALOGENATED AROMATIC HYDROCARBONS; HYDROCARBONS; KINETICS; ORGANIC COMPOUNDS; ORGANIC FLUORINE COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; POLYENES; REACTION KINETICS; SPECTRA; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Kurosawa, Hideo, Ohnishi, Hiroaki, Emoto, Mitsuhiro, Chatani, Naoto, Kawasaki, Yoshikane, Murai, Shinji, and Ikeda, Isao. Preparation and reductive elimination of (. eta. sup 3 -allyl)(aryl)nickel(II) complexes: Unusually facile. eta. sup 3 -allyl-aryl coupling on nickel having an 18-electron configuration. United States: N. p., 1990. Web. doi:10.1021/om00162a014.
Kurosawa, Hideo, Ohnishi, Hiroaki, Emoto, Mitsuhiro, Chatani, Naoto, Kawasaki, Yoshikane, Murai, Shinji, & Ikeda, Isao. Preparation and reductive elimination of (. eta. sup 3 -allyl)(aryl)nickel(II) complexes: Unusually facile. eta. sup 3 -allyl-aryl coupling on nickel having an 18-electron configuration. United States. https://doi.org/10.1021/om00162a014
Kurosawa, Hideo, Ohnishi, Hiroaki, Emoto, Mitsuhiro, Chatani, Naoto, Kawasaki, Yoshikane, Murai, Shinji, and Ikeda, Isao. 1990. "Preparation and reductive elimination of (. eta. sup 3 -allyl)(aryl)nickel(II) complexes: Unusually facile. eta. sup 3 -allyl-aryl coupling on nickel having an 18-electron configuration". United States. https://doi.org/10.1021/om00162a014.
@article{osti_5943772,
title = {Preparation and reductive elimination of (. eta. sup 3 -allyl)(aryl)nickel(II) complexes: Unusually facile. eta. sup 3 -allyl-aryl coupling on nickel having an 18-electron configuration},
author = {Kurosawa, Hideo and Ohnishi, Hiroaki and Emoto, Mitsuhiro and Chatani, Naoto and Kawasaki, Yoshikane and Murai, Shinji and Ikeda, Isao},
abstractNote = {The preparation and NMR spectral characterization of complexes of the type ({eta}{sup 3}-allyl)(aryl)(triphenylphosphine)nickel(II) (aryl = C{sub 6}H{sub 3}Cl{sub 2}-2,5, C{sub 6}F{sub 5}), 4, are described. Addition of PPh{sub 3} to a solution of 4 did not result in the formation of ({eta}{sup 1}-allyl)nickel intermediate as was deduced from {sup 1}H NMR measurements, in contrast to the ready conversion of ({eta}{sup 3}-allyl)palladium to ({eta}{sup 1}-allyl)palladium species. The (dichlorophenyl)nickel derivative underwent reductive elimination ca. 26 times as fast as the corresponding palladium complex. Addition of chelating diphosphine (Ph{sub 2}PCH{sub 2}CH{sub 2}PPh{sub 2}, (Z)-Ph{sub 2}PCH{double bond}CHPPh{sub 2}) to the solution of the above nickel complexes afforded stereochemically nonrigid 18-electron {eta}{sup 3}-allyl complexes, Ni({eta}{sup 3}-allyl)(aryl)(diphos), 5, which have been characterized by low-temperature {sup 1}H, {sup 13}C, and {sup 31}P NMR spectra for the C{sub 6}F{sub 5} analogues. This behavior is again different from that of the palladium analogue, which has an identical composition in which the 16-electron {eta}{sup 1}-allyl form is the ground-state structure. The kinetics of the reductive elimination of complexes 5 revealed that these undergo reductive elimination quite readily, with {Delta}H{sup {double dagger}} being ca. 60 kJ/mol lower than those values for the parent 16-electron counterparts 4. Also presented is evidence against the significant contribution of a short-lived 16-electron {eta}{sup 1}-allyl isomer of 5 to the enhanced reactivity with regard to the C-C coupling step in the diphosphine/allylnickel system.},
doi = {10.1021/om00162a014},
url = {https://www.osti.gov/biblio/5943772}, journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 9:12,
place = {United States},
year = {1990},
month = {12}
}