Reactivity of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine with CuI and [Cu(MeCN)4][PF6]: Benzimidazole Formation vs. Cu Oxidation

The reaction of 2,2′-Bis(2N-(1,1′,3,3′-tetramethyl-guanidino))diphenylene-amine (TMG2PA) (1) with CuI in MeCN results in the formation of [CuII(TMG2PAamid)I] (2) indicatingthat CuI is the target of an oxidative attack of the N-H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)4][PF6] is used as the CuI source, [CuI2(TMGbenz)2][PF6]2 (3) is obtained instead. The use of the non-coordinating counterion [PF6]– apparently prevents CuI from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole-guanidine ligand.

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