On the inverse trans influence. Density functional studies of [MOX5]n− (M = Pa, n= 2; M = U, n= 1; M = Np, n= 0; X = F, Cl or Br)

摘要: The geometric and electronic structures of [MOX5]n− (M = Pa, n = 2; M U, 1; Np, 0; X F, Cl or Br) have been investigated using relativistic density functional theory. An inverse trans influence (i.e. in which the An–Xcis distances are longer than An–Xtrans bonds) is found all cases, there good agreement with experimental structure [UOCl5]−. O–An–Xcis angle cases to be very close 90°, by contrast analogous transition metal systems this between 96° 102°, display a regular influence. Molecular orbital arguments presented account for difference at d- f-block systems, hence for their behaviour. Comparisons drawn previous explanations title systems. Mayer bond orders reported, used understand further metal–ligand interactions.