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Issue 6, 2002
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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)

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Abstract

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

Graphical abstract: 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)

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Publication details

The article was received on 23 Oct 2001, accepted on 28 Nov 2001 and first published on 07 Feb 2002


Article type: Paper
DOI: 10.1039/B109696F
Citation: J. Chem. Soc., Dalton Trans., 2002, 1233-1239
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    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)

    E. O'Grady and N. Kaltsoyannis, J. Chem. Soc., Dalton Trans., 2002, 1233
    DOI: 10.1039/B109696F

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