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 |
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Pages (from-to) | 4015-4023 |
Number of pages | 9 |
Journal | Inorganica Chimica Acta |
Volume | 357 |
Issue number | 13 |
DOIs | |
Publication status | Published - Nov 1 2004 |
Keywords
- Bond activation
- Nickel
- Pincer complexes
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry