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

Keywords

Bond activation
Nickel
Pincer complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2004.06.002

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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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TY - JOUR

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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JO - Inorganica Chimica Acta

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