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

Milko E. Van Der Boom; Shyh Yeon Liou; Linda J.W. Shimon; Yehoshoa Ben-David; David Milstein

doi:10.1016/j.ica.2004.06.002

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

Milko E. Van Der Boom, Shyh Yeon Liou, Linda J.W. Shimon, Yehoshoa Ben-David, David Milstein

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article

63 Citations (Scopus)

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 language	English
Pages (from-to)	4015-4023
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	357
Issue number	13
DOIs	https://doi.org/10.1016/j.ica.2004.06.002
Publication status	Published - Nov 1 2004

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Keywords

Bond activation
Nickel
Pincer complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Cite this

Van Der Boom, M. E., Liou, S. Y., Shimon, L. J. W., Ben-David, Y., & Milstein, D. (2004). Nickel promoted C-H, C-C and C-O bond activation in solution. Inorganica Chimica Acta, 357(13), 4015-4023. https://doi.org/10.1016/j.ica.2004.06.002

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

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.",

keywords = "Bond activation, Nickel, Pincer complexes",

author = "{Van Der Boom}, {Milko E.} and Liou, {Shyh Yeon} and Shimon, {Linda J.W.} and Yehoshoa Ben-David and David Milstein",

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T1 - Nickel promoted C-H, C-C and C-O bond activation in solution

AU - Van Der Boom, Milko E.

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.

KW - Bond activation

KW - Nickel

KW - Pincer complexes

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10.1016/j.ica.2004.06.002