4 years ago

Three-Coordinate Copper(II) Aryls: Key Intermediates in C–O Bond Formation

Three-Coordinate Copper(II) Aryls: Key Intermediates in C–O Bond Formation
Christine Greene, Subrata Kundu, Timothy H. Warren, Thomas R. Cundari, Jeffery A. Bertke, Tolani K. Salvador, Kamille D. Williams
Copper(II) aryl species are proposed key intermediates in Cu-catalyzed cross-coupling reactions. Novel three-coordinate copper(II) aryls [CuII]-C6F5 supported by ancillary β-diketiminate ligands form in reactions between copper(II) alkoxides [CuII]-OtBu and B(C6F5)3. Crystallographic, spectroscopic, and DFT studies reveal geometric and electronic structures of these Cu(II) organometallic complexes. Reaction of [CuII]-C6F5 with the free radical NO(g) results in C-N bond formation to give [Cu](η2-ONC6F5). Remarkably, addition of the phenolate anion PhO to [CuII]-C6F5 directly affords diaryl ether PhO-C6F5 with concomitant generation of the copper(I) species [CuI](solvent) and {[CuI]-C6F5}. Experimental and computational analysis supports redox disproportionation between [CuII]-C6F5 and {[CuII](C6F5)(OPh)} to give {[CuI]-C6F5} and [CuIII](C6F5)(OPh) unstable toward reductive elimination to [CuI](solvent) and PhO-C6F5.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b04046

DOI: 10.1021/jacs.7b04046

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