Uranium (VI)Bis(imido) chalcogenate complexes:synthesis and density functional theory analysis Page: 2 of 9
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Article1 Uranium(VI) Bis(imido) Chalcogenate Complexes: Synthesis and Density
2 Functional Theory Analysis
3 Liam P. Spencer,t Ping Yang,* Brian L. Scott,t Enrique R. Batista,* and James M. Boncella*.t
4 Materials, Physics and Applications Division, Los Alamos National Laboratory, MS J514,
5 Los Alamos, New Mexico 87545, and Theoretical Division, Los Alamos National Lahoratory,
6 MS B268, Los A/amos, New Mexico 87545
7 Received November 18, 2008
8 Bis(imido) uranium(VI) trans- and cis-dichalcogenate complexes with the general formula U(N'Bu)2(EAr)2(OPPh3)2
9 (EAr = O-2- BuCH4, SPh, SePh, TePh) and U(N Bu)2(EAr)2(R2bpy) (EAr = SPh, SePh, TePh) (R2bpy = 4,4'-
10 disubstituted-2,2'-bipyridyl, R = Me, Bu) have been prepared. This family of complexes includes the first reported
11 monodentate selenolate and tellurolate complexes of uranium(VI). Density functional theory calculations show that
12 covalent interactions in the U-E bond increase in the trans-dichalcogenate series U(N'Bu)2(EAr)2(OPPh)2 as the
13 size of the chalcogenate donor increases and that both 5f and 6d orbital participation is important in the M-E
14 bonds of U-S, U-Se, and U-Te complexes.15
The significance of covalent interactions and the role of
f-orbitals in metal ligand bonds in f-clement complexes is
an intensely studied and greatly debated area in actinide
chemistry. Studies of uranyl (UO--+) complexes have been
crucial in developing an understanding of the importance of
these issues in f-element complexes, in particular their
function in the formation of U=0 multiple bonds.' The
interactions of ligands in the equatorial plane perpendicular
to the dioxo ligands are also important because of the
relevance of the UO 2+ ion in lanthanide/actinide separation
schemes and speciation of the U022+ ion in the environment.
Coordination chemistry studies of this ion have shown that
the majority of complexes involve hard donor ligands (i.e.,
0, N, and halide)2 which suggests that the equatorial U-L
bonds possess significant ionic character. The coordination
of soft donor ligands to the UO22T ion holds promise for
' To whom correspondence should be addressed. E-mail: boncella@
Ian l.gov.
Materials, Physics and Applications Division.
Theoretical Division.
(1) (a) Grenthe. I. et. al. In The Chemnishry of the Actinide and Transac-
rinide E/ements, 3rd ed.: Morss. L. R., Edelstein. N. M., Fuger, J.,
Eds.: Springer-Verlag: New York, 2006: Vol. I. pp 253-698
(2) (a) Bagnall. K. W. I. In Comprehenstre Coordination Chemistr:v
Pcrgamon: Oxford. 1987: Vol. 3, p 1187. (b) King, R. B. J. Coord.
Chem. 2005, 58. 47. (c) Szabo. Z.: Toraishi, T.: Vallet, V.; Grenthe,
1. Coord. Chem. Rer. 2006. 250, 784.
(3) Pierloot. K.: san Besien. E. J. Chem. Phys. 2005, 123, 204309.10.1021/ic802212m CCC: $40.75 XXXX American Chemical Society
PAGE EST: 7.5further understanding covalency and f-orbital participation
in U-L bonding; however, few of these complexes have
been reported.
We have recently reported the isolation of the imido
analogue of the uranyl ion (U(NR)2-) and found that there
are some striking differences between this ion and the uranyl
ion.5 Density functional theory (DFT) calculations and X-ray
absorption near edge structure (XANES) experiments have
shown that there is less positive charge present on the
uranium center in the U(NR)22+ ion, which suggests a greater
degree of covalency in the U=N bond in comparison to the
U=0 bond in the U02" ion.5a We have also found that soft
phosphine donor ligands can coordinate to the U(NR)22+ ion
in contrast to the UO2- fragment.h" This finding suggests
that the metal center in the U(NR)22+ ion is a softer Lewis
acid than its UO22'+ counterpart which presents the op-
(4) (a) Kansan, S.: Barnes. C. L.: Duval. P. B. /norg. Chem. 2005. 44,
9137. (b) Crawford, M. J.; Ellern, A.: Noth. H.: Suter, M. J. Am. Chem.
Soc. 2003, /25, 11778. (c) Berthet, J. C.: Nierlich, M : Ephritikhine,
M. Chem. Common. 2004. 870 (d) Crawford. M. J.: Ellern. A.;
Karaghiosoff, K.; Mayer. P.: Noth. H.: Suter, M. inorg. Chem. 2004,
43. 7120. (e) Rose. D.; Chang, Y. D.; Chcn, Q.: Zubicta. J. Inorg.
Cheap. 1994. 3.3. 5167. (f) Rose, D. J.; Chen. Q.; Zubieta, J. /norg.
Chiu. Ac a 1998. 268, 163. (g) Crawford, M. J.: Mayer, P. hnorg.
Chem. 2005, 44, 5547.
(5) (a) Hayton, T. W.; Boncella, J. M.: Scott, B. L.; Palmer, P. D.; Batista,
E. R., Hay. P. J. Science 2005,3/0, 194 . (b) Hayton, T. W., Boncella.
J. M.; Scott, B L.; Batista, E. R J Am Chem. Soc 2006, 128, 10549.
(c) Spencer, L. P : Yang. P.; Scott, B. L.: Batista, E. R.; Boncella,
J. M. J. Am. Chem. Soc. 2008, 130, 2930 (d) Spencer, L. P.; Gdula,
R. L.; Hayton. T. W., Scott, B. L.; Batista, E. R.; Boncella, J. M.
Chem. Common. 2008. 4986.Inorganic Chemistry, Vol. xx, No. x, XXXX A
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Spencer, Liam P.; Batista, Enrique R.; Boncella, James M.; Yang, Ping & Scott, Brian L. Uranium (VI)Bis(imido) chalcogenate complexes:synthesis and density functional theory analysis, article, January 1, 2009; [New Mexico]. (https://digital.library.unt.edu/ark:/67531/metadc934189/m1/2/: accessed April 23, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.