Nickel promoted C-H, C-C and C-O bond activation in solution

Milko van der Boom, Shyh Yeon Liou, Linda J W Shimon, Yehoshoa Ben-David, David Milstein

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Abstract

Reaction of NiI2 with the PCP-ligand {1-Et-2,6-(CH 2PiPr2)2-C6H 3} (1) results in selective activation of the strong sp 2-sp3 aryl-ethyl bond to afford the aryl-nickel complex [Ni{2,6-(CH2PiPr2)2-C 6H3}I] (2), whereas reaction of NiI2 with {1,3,5-(CH3)3-2,6-(CH2PiPr 2)2-C6H} (4) leads to the formation of the benzylic complex [Ni{1-CH2-2,6-(CH2PiPr 2)2-3,5-(CH3)2-C6H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni{2,6-(CH2PiPr2)2-3,5-(CH 3)2-C6H}I] (6) by activation of the sp 2-sp3 C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI2 with {1,3-(CH2PiPr2)2-C6H 4} (3) and {1,3-(CH3)2-4,6-(CH 2PiPr2)2-C6H 2} (7), respectively, lacking the aryl-alkyl groups between the "phosphines arms" (alkyl=ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine {1-OMe-2,6-(CH2PiPr2)2-C 6H3} (8) with NiI2 results in the formation of the phenoxy complex [Ni{1-O-2,6-(CH2PiPr2) 2-C6H3}I] (9) by selective sp 3-sp3 C-O bond activation.

Original languageEnglish
Pages (from-to)4015-4023
Number of pages9
JournalInorganica Chimica Acta
Volume357
Issue number13
DOIs
Publication statusPublished - Nov 1 2004

Fingerprint

Nickel
Chemical activation
nickel
activation
Phosphines
methylidyne
X-Rays
Electrons
Ligands
Thermolysis
X ray analysis
phosphines
ligands
electrons
x rays
single bond

Keywords

  • Bond activation
  • Nickel
  • Pincer complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Nickel promoted C-H, C-C and C-O bond activation in solution. / van der Boom, Milko; Liou, Shyh Yeon; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David.

In: Inorganica Chimica Acta, Vol. 357, No. 13, 01.11.2004, p. 4015-4023.

Research output: Contribution to journalArticle

van der Boom, Milko ; Liou, Shyh Yeon ; Shimon, Linda J W ; Ben-David, Yehoshoa ; Milstein, David. / Nickel promoted C-H, C-C and C-O bond activation in solution. In: Inorganica Chimica Acta. 2004 ; Vol. 357, No. 13. pp. 4015-4023.
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abstract = "Reaction of NiI2 with the PCP-ligand {1-Et-2,6-(CH 2PiPr2)2-C6H 3} (1) results in selective activation of the strong sp 2-sp3 aryl-ethyl bond to afford the aryl-nickel complex [Ni{2,6-(CH2PiPr2)2-C 6H3}I] (2), whereas reaction of NiI2 with {1,3,5-(CH3)3-2,6-(CH2PiPr 2)2-C6H} (4) leads to the formation of the benzylic complex [Ni{1-CH2-2,6-(CH2PiPr 2)2-3,5-(CH3)2-C6H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni{2,6-(CH2PiPr2)2-3,5-(CH 3)2-C6H}I] (6) by activation of the sp 2-sp3 C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI2 with {1,3-(CH2PiPr2)2-C6H 4} (3) and {1,3-(CH3)2-4,6-(CH 2PiPr2)2-C6H 2} (7), respectively, lacking the aryl-alkyl groups between the {"}phosphines arms{"} (alkyl=ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine {1-OMe-2,6-(CH2PiPr2)2-C 6H3} (8) with NiI2 results in the formation of the phenoxy complex [Ni{1-O-2,6-(CH2PiPr2) 2-C6H3}I] (9) by selective sp 3-sp3 C-O bond activation.",
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AU - van der Boom, Milko

AU - Liou, Shyh Yeon

AU - Shimon, Linda J W

AU - Ben-David, Yehoshoa

AU - Milstein, David

PY - 2004/11/1

Y1 - 2004/11/1

N2 - Reaction of NiI2 with the PCP-ligand {1-Et-2,6-(CH 2PiPr2)2-C6H 3} (1) results in selective activation of the strong sp 2-sp3 aryl-ethyl bond to afford the aryl-nickel complex [Ni{2,6-(CH2PiPr2)2-C 6H3}I] (2), whereas reaction of NiI2 with {1,3,5-(CH3)3-2,6-(CH2PiPr 2)2-C6H} (4) leads to the formation of the benzylic complex [Ni{1-CH2-2,6-(CH2PiPr 2)2-3,5-(CH3)2-C6H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni{2,6-(CH2PiPr2)2-3,5-(CH 3)2-C6H}I] (6) by activation of the sp 2-sp3 C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI2 with {1,3-(CH2PiPr2)2-C6H 4} (3) and {1,3-(CH3)2-4,6-(CH 2PiPr2)2-C6H 2} (7), respectively, lacking the aryl-alkyl groups between the "phosphines arms" (alkyl=ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine {1-OMe-2,6-(CH2PiPr2)2-C 6H3} (8) with NiI2 results in the formation of the phenoxy complex [Ni{1-O-2,6-(CH2PiPr2) 2-C6H3}I] (9) by selective sp 3-sp3 C-O bond activation.

AB - Reaction of NiI2 with the PCP-ligand {1-Et-2,6-(CH 2PiPr2)2-C6H 3} (1) results in selective activation of the strong sp 2-sp3 aryl-ethyl bond to afford the aryl-nickel complex [Ni{2,6-(CH2PiPr2)2-C 6H3}I] (2), whereas reaction of NiI2 with {1,3,5-(CH3)3-2,6-(CH2PiPr 2)2-C6H} (4) leads to the formation of the benzylic complex [Ni{1-CH2-2,6-(CH2PiPr 2)2-3,5-(CH3)2-C6H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni{2,6-(CH2PiPr2)2-3,5-(CH 3)2-C6H}I] (6) by activation of the sp 2-sp3 C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI2 with {1,3-(CH2PiPr2)2-C6H 4} (3) and {1,3-(CH3)2-4,6-(CH 2PiPr2)2-C6H 2} (7), respectively, lacking the aryl-alkyl groups between the "phosphines arms" (alkyl=ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine {1-OMe-2,6-(CH2PiPr2)2-C 6H3} (8) with NiI2 results in the formation of the phenoxy complex [Ni{1-O-2,6-(CH2PiPr2) 2-C6H3}I] (9) by selective sp 3-sp3 C-O bond activation.

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KW - Nickel

KW - Pincer complexes

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