UC San Diego

Copyright © 2014 John Wiley & Sons, Ltd. The structure and dynamics of five-coordinate iridacyclopentadiene-chlorido and -hydrido complexes of the form [(PH 3 ) 2 Ir(CY = CYCY′ = CY′)X] (X = Cl or H and Y = F and/or H) are investigated by M06-2X/Def2-TZVPP density functional theory computation. For the symmetrically substituted ring systems (Y = Y′ = H and Y = Y′ = F) the minimum energy chlorido structures are Y-shaped trigonal bipyramids; whereas the hydrido complexes favor a T-structure. Both the symmetrically and unsymmetrically (Y = H, Y′ = F) substituted hydrido complexes exhibit double well potentials for the hydrido ligand wag motion within the metallacycle ring plane, the depths of the well depending on the degree of steric, and electronic interactions within the particular constitutional isomer.