Intramolecular C−H Activation Directed Self-Assembly of an Organoplatinum(II) Molecular Square

A Pt(II) complex that contains a N,N-chelate ligand with the formula of Pt(NPA)(CH3)2 (1), NPA = N-(2‘-pyridyl)-7-azaindole, has been found to undergo a rapid chelate ring opening and “roll-over” process that leads to intramolecular C−H activation and the subsequent formation of a rare organoplatinum Pt4 macrocycle, Pt4(CH3)4(N,C,N-NPA)4 (2), without extra linkers. Complex 2 has been fully characterized by NMR, elemental, and X-ray diffraction analyses. Kinetic study using NMR spectroscopy has established that, in the absence of strong coordinating solvent molecules, the rate-determining step for the conversion process of 1 to 2 is the C−H cleavage step, and 2 is formed exclusively. The presence of strong coordinating solvent molecules, such as CH3CN, terminates the reaction at the Pt(CH3)(N,C-NPA)(L) formation step where L = the solvent molecule. The facile roll-over intramolecular C−H activation and the facile and selective formation of the cyclic Pt4 complex by compound 1 are attributed to the poor stability of the N,N-chelate mode and the geometry of NPA.