Computational study of equilibria formed by diiodine (I2) and the pincer complex [2,6‐bis{(Me2NCH2)2}C6H3]PtIII: intramolecular mobility of I2 using 'Pt‐I2', 'Pt‐I···I2' and 'C para ···I2' species

DFT computation indicates the presence of solution equilibria with very low barriers when diiodine interacts with the square‐planar platinum(II) pincer complex Pt(NCN)I (NCN=[2,6‐bis{(dimethylamino)methyl}phenyl‐ N,C,N ] − ) in dichloromethane. Species present include square‐planar Pt(NCN)(η 1 ‐I 3 ) and square‐pyramidal Pt(NCN)I(η 1 ‐I 2 ) interconverted via a triangular transition state with I 2 bridging a Pt−I bond, and interaction of diiodine at the para ‐position of the arene ring interconverted with Pt(NCN)I(η 1 ‐I 2 ) via a transition state with diiodine bridging the C ortho ‐ and C meta ‐positions. Similar facile intramolecular rearrangements occur for a model system with a molar ratio of 1 : 2 for Pt : I 2 , exhibiting species such as Pt(NCN)(η 1 ‐I 3 )(η 1 ‐I 2 ) and mobility of diiodine over the (pincer)PtI plane.