Aromatic C-H Activation in the Triplet Excited State of Cyclometalated Platinum(II) Complexes Using Visible Light

作者：Julia Fabio; Gonzalez Herrero Pablo

来源：Journal of the American Chemical Society, 2016, 138(16): 5276-5282.

DOI：10.1021/jacs.5b13311

The visible-light driven cyclometalation of arene substrates containing an N-donor heteroaromatic moiety as directing group by monocyclometalated Pt(II) complexes is reported. Precursors of the type [PtMe(C boolean AND N)(N boolean AND CH)], where N boolean AND CH is 2-phenylpyridine (ppyH) or related compunds with diverse electronic properties and CAN is the corresponding cyclometalated ligand, afford homoleptic cis-[Pt(C boolean AND N)(2)] complexes upon irradiation with blue LEDs at room temperature with evolution of methane. Heteroleptic derivatives cis-[Pt(ppy)(C'boolean AND N')] are obtained analogously from [PtMe(ppy)(N'boolean AND C'H)], where N'boolean AND C'H represents an extended set of heteroaromatic compounds. Experimental and computational studies demonstrate an unprecedented C-H oxidative addition, which is initiated by a triplet excited state of metal-to-ligand charge-transfer (MLCT) character and leads to a detectable Pt(IV) methyl hydride intermediate.

• 出版日期2016-4-27