Phosphine and Selenoether -Substituted Acenaphthenes and Their Transition-Metal Complexes: Structural and NMR Investigations.

A series of -substituted acenaphthene-based phosphine selenoether bidentate ligands Acenap(PrP)(SeAr) (-, Acenap = acenaphthene-5,6-diyl, Ar = Ph, mesityl, 2,4,6-trisopropylphenyl and supermesityl) were prepared. The rigid acenaphthene framework induces a forced overlap of the phosphine and selenoether lone pairs, resulting in a large magnitude of through-space coupling, ranging from 452 to 545 Hz. These rigid ligands - were used to prepare a series of selected late d-block metals, mercury, and borane complexes, which were characterized, including by multinuclear NMR and single-crystal X-ray diffraction.