Nickel promoted C-H, C-C and C-O bond activation in solution |
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| Authors: | Milko E van der Boom Shyh-Yeon Liou Yehoshoa Ben-David |
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| Institution: | a Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel
b Unit of Chemical Research Support, The Weizmann Institute of Science, Rehovot 76100, Israel |
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| Abstract: | Reaction of NiI2 with the PCP-ligand {1-Et-2,6-(CH2PiPr2)2-C6H3} (1) results in selective activation of the strong sp2-sp3 aryl-ethyl bond to afford the aryl-nickel complex Ni{2,6-(CH2PiPr2)2-C6H3}I] (2), whereas reaction of NiI2 with {1,3,5-(CH3)3-2,6-(CH2PiPr2)2-C6H} (4) leads to the formation of the benzylic complex Ni{1-CH2-2,6-(CH2PiPr2)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-(CH3)2-C6H}I] (6) by activation of the sp2-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-C6H4} (3) and {1,3-(CH3)2-4,6-(CH2PiPr2)2-C6H2} (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-C6H3} (8) with NiI2 results in the formation of the phenoxy complex Ni{1-O-2,6-(CH2PiPr2)2-C6H3}I] (9) by selective sp3-sp3 C-O bond activation. |
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| Keywords: | Nickel Pincer complexes Bond activation |
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