Oxidatively Induced Reductive Elimination from a Chromium(III) Bis(aryl) Complex
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The previously reported high-spin Cr(II) compounds CpCr(C6H4CH2NMe2) (1) and CpCr[C(Ph)C(Ph)C6H4CH2NMe2] (2) were investigated as precursors to CpCr(III) complexes. Single-electron oxidation of 1 was used to prepare CpCr(C6H4CH2NMe2)(X) for X = I (3), OTs (4), O2CPh (5), OCMe2Ph (6), SPh (7). Similarly, CpCr[C(Ph)C(Ph)C6H4CH2NMe2](X) for X = I (8), SPh (9) were obtained from 2. Reactions of 4 with PhCH2MgCl or Mg(C6H4Me)2 reagents gave the Cr(III) benzyl (10) and p-tolyl (11) complexes, respectively. The corresponding reaction of 4 with Mg(CH2CMe3)2 led to isolation of 12, a bimetallic complex with a bridging neopentylidene group. While the reaction of 7 or 10 with AgOTs gave Cr(III) tosylate complex 4, the reaction of 11 and AgOTs led to the product of reductive elimination. The structures of 1, 2, 6–8, 11, and 12 were elucidated using single-crystal X-ray diffraction.
